Fragrance mixtures

ABSTRACT

Suggested is a fragrance mixture comprising specific esters of (−)-carveol and/or (−)-dihydro-carveol.

FIELD OF INVENTION

The present invention belongs to the area of scents and refers to newfragrance mixtures, their preparation and use in perfume andend-consumer compositions.

STATE OF THE ART

Perfume industry constantly requires new scent creations. Creating a newfragrance or perfume is associated with quite a number of challenges.For example, it is necessary to pick a specific composition of fewscents out of a nearly unlimited number of possible structures know fromthe state of the art to satisfy a concrete need of the market and toprovide a product that matches with the specific profile needed by thecustomer. Often, suitable scents show very advantageous performancehowever in combination with unpleasant and thus disadvantageousolfactory aspects, making it difficult or even impossible to use themfor the specific purpose.

A second important problem refers to the need for providing scentcompositions which not only match with a specific olfactory profile, butalso provides so-called secondary advantageous properties. As a matterof fact, many fragrance compositions known from the market exhibitsignificant disadvantages in application, for example poor solubilityand stability over storage, but also failures with regard to subjectiveissues like plentifulness, charisma and the like. In addition, a lot ofknown fragrance compositions require high dosages to achieve the desiredolfactory result. Another prerequisite for fragrances nowadays is highbiodegradability and dermatological and toxicological safety.

L-carvyl acetate (1-para-mentha-6,8-dien-2-yl acetate) has beendescribed first in 1969 by S. Arctander (see: “Perfume and FlavourChemicals, Vol. 1+11, Montclair, N.J., No. 582). Its trans-isomer isregarded as a natural component of spearmint oil. It provides a fresh,green-mint scent with a slight metallic aspect. The same paper makesreference to l-carvyl propionate (l-para-mentha-6,8-dien-2-ylpropionate, No. 583) its scent being described as sweet, warm, mint,herbaceous with a smooth sub-note. No. 929 exhibits the scent ofdihydrocarvyl acetate (para-menth-8-(9)-en-2yl-acetate;6-menthyl-3-iso-propenyl-cyclohexanyl-acetate) as being sweet, slightlymint, bloomy, and rose-like with an herbaceous sub-note.

Zhao et al. describe variations of essential menthe oils from Chinacontaining carveol and carveol derivatives, but with no disclosureconcerning the specific isomers (Industrial Crops and products, Vol. 42,p. 251-260 (2013). A similar paper concerning the composition ofCalamintha was published by Monforte et al. The document however is alsosilent with regard to specific carveol isomers (J. Medicinal Food, Vol.14(3), p. 297-303 (2011).

The object underlying the present invention has been providing a newfragrance mixture with the capability to improve positive andadvantageous olfactory aspects of a fragrance and/or (simultaneously)decreasing, inhibiting and/or masking unwanted unpleasant olfactoryaspects and sub-notes of fragrances. More particularly, the newfragrance mixtures should be characterised by improving stability,solubility and overall performance of fragrances as well as reducing therequired dosage. Finally, the mixtures itself should exhibit excellentbiodegradability and should be safe to humans and environment.

DESCRIPTION OF THE INVENTION

A first object of the present invention is a fragrance mixturecomprising

-   (a) at least one compound of general formula (I)

in which R₁ stands for methyl, ethyl, methoxy or ethoxy;

-   (b) at least one compound of general formula (II)

in which R₂ stands for methyl, ethyl, methoxy or ethoxy;

-   (c) at least one additional fragrance, different from compounds (I)    and (II); and-   (d) optionally at least one solvent.

Preferably the mixture comprises as component (b) a compound of generalformula (IIa)

in which R₂ stands for methyl, ethyl, methoxy or ethoxy.

Surprisingly, it has been observed that mixtures according to thepresent invention are capable of supporting, increasing and/or improvingolfactory properties of other fragrances, while simultaneously reducing,inhibiting and/or completely masking negative, unpleasant sub-notes ofthese scents. This is opposite to what a skilled person would haveexpected, since the compositions themselves do not exhibit a pleasantscent at all; the opposite is the case. For example, mixtures of[(1S,5S)-5-isopropenyl-2-methyl-cyclohexyl] acetate and[1S,5S)-5-isopropenyl-2-methyl-cyclohex-2-en-1-yl] acetate exhibit ascent that can be described as being metallic, oily, technical,sulphurous, garlic-like and carbide-like. However, when combined withother top-note fragrances these unpleasant notes are no longerrecognized, in contrast, unpleasant sub-notes of said top notefragrances are reduced or even completely masked. The compoundsaccording formulae (I) and (II) are completely biodegradable, safe tohuman and environment, easy to dissolve, storage-stable and improveimpact and over-all performance and reduce dosage when blended withother fragrances.

Additional Fragrances

The additional fragrances forming group (c) are preferably chosen fromthe group consisting of terpenes, aldehydes, nitriles, esters, lactonesand mixtures thereof. More particularly, said additional fragrances showa molecular mass of about 100 to about 250 Dalton. Suitable examplesencompass members from the following groups:

Aldehydes

Examples for suitable fragrances showing an aldehyde structure encompassmelonal, triplal, ligustral, adoxal, anisaldehyde, cymal, ethylvanillin,florhydral, floralozon, helional, heliotropin, hydroxycitronellal,koavon, laurinaldehyde, canthoxal, lyral, lilial, adoxal, anisaldehyde,cumal, methyl-nonyl-acetaldehyde, citronellal,citronellyloxy-acetaldehyde, cyclamenaldehyde, bourgeonal,p-tert.-bucinal, phenylacetaldehyde, undecylenaldehyde, vanillin;2,6,10-trimethyl-9-undecenal, 3-dodecen-l-al, α-n-Amylzimtaldehyde,4-methoxy-benzaldehyde, benzaldehyde,3-(4-tert-butylphenyl)-propanal,2-methyl-3-(para-methoxy-phenylpropanal),2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal,3-phenyl-2-propenal,cis-/trans-3,7-dimethyl-2,6-octadien-l-al,3,7-dimethyl-6-octen-l-al,[(3,7-dimethyl-6-octenyl)-xy]-cetaldehyde,4-isopropylbenzyaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxyaldehyde,2-methyl-3-(isopropyl-phenyl)propanal, decyl aldehyde,2,6-dimethyl-5-heptenal; 4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal;octahydro-4,7-methano-IH-indenecarboxaldehyde;3-ethoxy-4-hydroxybenzaldehyde,para-ethyl-alpha,alpha-dimethylhydrozimtaldehyde,α-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,3,4-methylenedioxybenzaldehyde, α-n-hexyl-cinnamaldehyde,m-cymene-7-carboxaldehyde, α-methylphenylacetaldehyde,7-hydroxy-3,7-dimethyl octanal, undecenal,2,4,6-trimethyl-3-cyclohexene-l-carboxalde-hyde,4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,2,4-dimethyl-cyclohexene-3-carboxaldehyde,4-(4-hydroxy-4-methylpentyl)-3-cylohexene-l-carboxal-dehyde,7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal,1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal,2-methyl-3-(4-tertbutyl)propanal,3-(4-ethylphenyl)-2,2-dimethylpropanal,3-(4-methoxyphenyl)-2-methylpropanal, methylnonylacetaldehyde,2-phenylpropan-1-al, 3-phenylprop-2-en-1-al,3-phenyl-2-pentylprop-2-en-1-al, 3-phenyl-2-hexylprop-2-enal,3-(4-isopropylphenyl)-2-methylpropan-1-al,3-(4-ethylphenyl)-2,2-dimethylpropan-1-al,3-(4-tert-butylphenyl)-2-methyl-propanal,3-(3,4-Methylendioxy-phenyl)-2-methylpropan-1-al,3-(4-Ethylphenyl)-2,2-dimethylpropanal,3-(3-Isopropylphenyl)-butan-1-al,2,6-Dimethylhept-5-en-1-al,Dihydrozimtaldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5- or6-Methoxyhexahydro-4,7-methanoindan-1 or 2-carboxyaldehyde,3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,4-hydroxy-3-methoxybenzaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclohexene-carboxyaldehyde,7-hydroxy-3,7-dimethyl-octanal; trans-4-decenal, 2,6-nonadienal,p-tolylacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,o-methoxyzimtaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde,3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde;5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al),hexahydro-4,7-methanoindan-1-carboxaldehyde, octanal, 2-methyl octanal,alpha-methyl-4-(l-methylethyl)benzene-acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, p-methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal,hexahydro-8,8-dimethyl-2-naphthaldehyde,3-propyl-bicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal,3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde,1-p-menthene-q-carboxaldehyde, citral or its mixtures, lilial citral,1-decanal, n-undecanal, n-dodecanal, hlorhydral,2,4-dimethyl-3-cyclohexen-1-carboxaldehyde 4-methoxybenzaldehyde,3-methoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde,3,4-methylendioxybenzaldehyde, 3,4-dimethoxybenzaldehyde and theirmixtures.

As explained above, said ketones or said aldehydes may show analiphatic, cycloaliphatic, aromatic, ethylenically unsaturated structureor a mixture of these elements. The components may also includeheteroatoms or show a polycyclic structure. Suitable substituents forall these structures are hydroxyl and/or amino groups. Furtherfragrances are compiled in the following document: Steffen Arctander“Published 1960 and 1969 respectively, Reprinted2000 ISBN: AromaChemicals Vol. 1: 0-931710-37-5, Aroma Chemicals Vol. 2: 0-931710-38-3”,which is hereby incorporated by reference.

Ketones

Examples for suitable fragrances showing a ketone structure encompassbuccoxime, iso jasmone, methyl beta naphthyl ketone, moschus indanone,tonalid/moschus plus, α-damascone, β-damascon, δ-damascone,Iso-damascone, damascenone, damarose, methyl-dihydrojasmonate, menthone,carvone, campher, fenchone, alphalonen, β-iononw, dihydro-β-lonone,γ-methylionone, fleuramone, dihydrojasmone, cis-Jasmon, iso-E-Super,methyl cedrenylk etone, or methyl cedrylon, acetophenone, methyl acetophenone, p-methoxyacetophenone, methyl-β-naphtyl ketone, benzylacetone,benzophenone, p-hydroxy phenylbutanone, celery Ketone or livescon,6-osopropyl-deca-hydro-2-naphtone, dimethyloctenone, freskomenth,4-(l-ethoxyvinyl)-3,3,5,5,-tetramethylv cyclohexanone, methylheptenone,2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone,1-(p-menthene-6(2)-yl)-1-propanone,4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,2-Acetyl-3,3-dimethyl-norbornan,6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 4-damascol, dulcinylor cassione, gelsone, hexalone, isocyclemone E, Methylcyclocitrone,methyl lavender ketone, orivone, p-tert-butyl cyclohexanone, verdone,delphone, muscone, neobutenone, plicatone, veloutone,2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran, hedion and theirmixtures. The preferred ketones are selected from the group comprisingα-damascone, δ-damascone, iso-damascone, carvone, γ-methyl ionone,Iso-E-Super, 2,4,4,7-tetramethyl-oct-6-en-3-one, benzylacetone,β-damascone, damascenone, methyl dihydrojasmonate, methyl cedrylone,hedione and their mixtures

Alcohols

Suitable fragrance alcohols encompass for example 10-undecen-1-ol,2,6-dimethylheptan-2-ol, 2-methylbutanol,2-methylpentanol,2-phenoxyethanol, 2-phenylpropanol,2-tert-Butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol,3-methyl-5-phenylpentanol, 3-octanol, 1-octen-3-ol,3-phenylpropanol,4-heptenol, 4-isopropylcyclohexanol,4-tert-butycyclohexanol, 6,8-dimethyl-2-nonanol,6-nonen-1-ol,9-decen-1-ol, α-methyl benzylalcohol, α-terpineol, amylsalicylat, benzylalcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol,cyclohexyl salicylate, decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethyl heptanol, dimethyl octanol, ethyl salicylate,ethyl vanilin, anethol, eugenol, geraniol, heptanol, hexyl salicylat,isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol,n-hexanol, nerol, nonanol, octanol, para-menthan-7-ol,phenylethylalkohol, phenol, phenyl salicylat, tetrahydro geraniol,tetrahydro linalool, thymol, trans-2-cis-6-nonadienol,trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnamalcoholand their mixtures.

Esters

Examples for suitable fragrances showing a ketone structure encompassbenzyl acetate, phenoxyisobutyrate, p-tert.-butylcyclohexylacetate,linalylacetate, dimethylbenzyl-carbinylacetate (DMBCA),phenylethylacetate, benzylacetate, ethylmethylphenylglycinate,allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate,cyclohexylsalicylate, floramat, melusat, jasmacyclatat and theirmixtures.

Ethers

Examples for suitable fragrances showing a ketone structure encompassbenzylethyl ether or ambroxan

Hydrocarbons

Examples for suitable fragrances representing hydrocarbons encompassterpenes, e.g. limonen and pinen.

Solvents

Suitable solvents forming component (d) are sometimes advantageous toimprove compatibility of the mixtures of compounds (I) and (II) with theadditional fragrances.

Preferably said solvents represent alcohols, ether s or esters, such asethanol, isopropyl alcohol, ethylene glycol, diethylene glycol,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,propylene glycol, dipropylene glycol, 1,2-butylene glycol, glycerol,diethyl phthalate, triethyl citrate, isopropyl myristate and itsmixtures.

Mixtures

The compounds according formulae (I) and (II) are individually knownfrom the state of the art. Preferred compounds according formula (I)encompass for example:

-   -   [(1R,5R)-5-Isopropenyl-2-methyl-cyclohex-2-en-1-yl] acetate,    -   [(1R,5R)-5-Isopropenyl-2-methyl-cyclohex-2-en-1-yl] propionate,    -   [(1R,5R)-5-Isopropenyl-2-methyl-cyclohex-2-en-1-yl] methyl        carbonate,    -   [(1R,5R)-5-Isopropenyl-2-methyl-cyclohex-2-en-1-yl] ethyl        carbonate.

Preferred compounds of formula (II) comprise for example:

-   -   [(1S,5R)-5-Isopropenyl-2-methyl-cyclohexyl] acetate,    -   [(1S,5R)-5-Isopropenyl-2-methyl-cyclohexyl] propionate,    -   [(1S,5R)-5-Isopropenyl-2-methyl-cyclohexyl] methylcarbonate,    -   [(1S,5R)-5-Isopropenyl-2-methyl-cyclohexyl] ethylcarbonate,

As indicated above, the preferred species within group (b) are describedby formula (IIa). More particularly the mixtures comprise the followingindividuals:

-   -   [(1R,2R,5R)-5-Isopropenyl-2-methyl-cyclohexyl] acetate,    -   [(1R,2R,5R)-5-Isopropenyl-2-methyl-cyclohexyl] propionate,    -   [(1R,2R,5R)-5-Isopropenyl-2-methyl-cyclohexyl] methylcarbonate,    -   [(1R,2R,5R)-5-Isopropenyl-2-methyl-cyclohexyl] ethylcarbonaet,

Preferably the mixture of the present invention comprise said components(a) and (b) in a ratio by weight of from about 1:99 to about 99:1, morepreferably in a ratio by weight of from about 10:90 to about 90:10 andparticularly in a ratio by weight of from about 51:49 to about 95:5.

In another preferred embodiment of the present invention the mixturesfurther comprise at least one compound of formula (III)

in which R₃ stands for methyl, ethyl, methoxy or ethoxy and the dottedline means a single or double bond.

The present invention also refers to a mixture comprising

-   (i) about 62 to about 67% b.w. of at least one 1R,5R isomer of    compound (I);-   (ii) about 14 to about 18% b.w. of at least one 1R,2R,5R isomer of    compound (IIa);-   (iii) about 6.0 to about 7.0% b.w. of at least one 1S,2R,5S isomer    of compound (II);-   (iv) about 7.0 to about 9.0% b.w. of at least one 1R,5S isomer of    compound (III);-   (v) about 4.0 to about 6.0% b.w. of at least one 1R,2S,5S isomer of    formula (III); and-   (vi) about 0.5 to about 1.0% b.w. of at least one 1R,2R,5S isomer of    formula (III) on condition that the amounts add to 100% b.w.

Carveol Esters

As indicated above, individual carveol esters are known from the stateof the art. For example, U.S. Pat. No. 2,803,647 (GLIDDEN CO.) disclosesa process for obtaining dihydrocarvyl esters by pyrolysis of a diesterof dihydrosoberol. This process requires high temperatures and aspecific reactor and is therefore disadvantageous for industrialproduction.

Another object of the present invention is therefore related to a newprocess for manufacturing of any of compounds (I), (II) and/or (III)comprising the following steps:

-   (A) providing a source of (−)-carveol and/or (−)-dihydrocarveol;-   (B) reacting said source of (−)-carveol and/or (−)-dihydrocarveol    with a compound of general formula (IV)

in which R₄ stands for a chlorine, methyl or ethyl group and R₅ isselected from a methyl, ethyl, acetyl or propionyl group to form anester.

Preferably, compound (IV) is selected from with methyl chloroformate,ethyl chloroformate, acetic anhydride or propionic anhydride

A preferred embodiment of the present invention refers to a processwherein a mixture of (−)-carveol and (−)-dihydrocarveol is reacted withmethyl chloroformate, ethyl chloroformate, acetic anhydride or propionicanhydride to form an ester, said (−)-carveol and (−)-dihydrocarveolbeing present in a ratio by weight of from about 1:99 to about 99:1,preferably about 10:90 to about 90:10 and particularly about 51:49 toabout 95:5 wherein the pH-value during the esterification is maintainedbetween about 6 and about 9.

Perfume Compositions

Another object of the present invention is related to a perfumecomposition comprising or consisting of the fragrance mixtureencompassing components (a), (b), (c) and optionally (d) as describedabove. Preferably, said composition may comprise about 0.001 to about75% b.w., more preferably about 0.01 to about 50% b.w. and particularlyabout 0.1 to about 5% b.w. of the mixture of compounds (I) and (II). Theperfume compositions may be applied directly to skin or for example asraw material for perfume oils, perfume extracts, eau de toilettes, aftershaves, eau de colognes, pre-shave products, splash colognes and airrefresher. Its major advantage can be seen it their high compatibilitywith various additives.

Cosmetic Compositions

Another object of the present invention refers to cosmetic or personalcare compositions either comprising the mixture of components (a), (b),(c) and optionally (d) as described above or the perfume compositionscomprising them. The cosmetic or personal care composition may representa skin care, hair care and/or sun care product, such as for example acosmetic cream, lotion, spray, emulsion, ointment, gel or mouse and thelike. Typical examples are skin creams and hair shampoos,antiperspirants and soaps.

The preparations according to the invention may contain abrasives,anti-acne agents, agents against ageing of the skin, anti-cellulitisagents, antidandruff agents, anti-inflammatory agents,irritation-preventing agents, irritation-inhibiting agents,antioxidants, astringents, perspiration-inhibiting agents, antisepticagents, ant-statics, binders, buffers, carrier materials, chelatingagents, cell stimulants, cleansing agents, care agents, depilatoryagents, surface-active substances, deodorizing agents, antiperspirants,softeners, emulsifiers, enzymes, essential oils, fibres, film-formingagents, fixatives, foam-forming agents, foam stabilizers, substances forpreventing foaming, foam boosters, gelling agents, gel-forming agents,hair care agents, hair-setting agents, hair-straightening agents,moisture-donating agents, moisturizing substances, moisture-retainingsubstances, bleaching agents, strengthening agents, stain-removingagents, optically brightening agents, impregnating agents,dirt-repellent agents, friction-reducing agents, lubricants,moisturizing creams, ointments, opacifying agents, plasticizing agents,covering agents, polish, gloss agents, polymers, powders, proteins,re-oiling agents, abrading agents, silicones, skin-soothing agents,skin-cleansing agents, skin care agents, skin-healing agents,skin-lightening agents, skin-protecting agents, skin-softening agents,hair promotion agents, cooling agents, skin-cooling agents, warmingagents, skin-warming agents, stabilizers, UV-absorbing agents, UVfilters, detergents, fabric conditioning agents, suspending agents,skin-tanning agents, thickeners, vitamins, oils, waxes, fats,phospholipids, saturated fatty acids, mono- or polyunsaturated fattyacids, α-hydroxy acids, polyhydroxyfatty acids, liquefiers, dyestuffs,colour-protecting agents, pigments, anti-corrosives, aromas, flavouringsubstances, odoriferous substances, polyols, surfactants, electrolytes,organic solvents or silicone derivatives and the like as additionalauxiliaries and additives.

Surfactants

Preferred auxiliaries and additives are anionic and/or amphoteric orzwitterionic surfactants. Typical examples of anionic surfactants aresoaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates,alkylether sulfonates, glycerol ether sulfonates, methyl estersulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ethersulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide(ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylicacids and salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids such as, forexample, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulfates, protein fatty acidcondensates (particularly wheat-based vegetable products) and alkyl(ether) phosphates. If the anionic surfactants contain polyglycol etherchains, they may have a conventional homolog distribution although theypreferably have a narrow-range homolog distribution. Typical examples ofamphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines. The surfactants mentioned are all knowncompounds. Information on their structure and production can be found inrelevant synoptic works, cf. for example J. Falbe (ed.), “Surfactants inConsumer Products”, Springer Verlag, Berlin, 1987, pages 54 to 124 or J.Falbe (ed.), “Katalysatoren, Tenside and Mineraloladditive (Catalysts,Surfactants and Mineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978,pages 123-217. The percentage content of surfactants in the preparationsmay be from 0.1 to 10% by weight and is preferably from 0.5 to 5% byweight, based on the preparation.

Oil Bodies

Suitable oil bodies, which form constituents of the O/W emulsions, are,for example, Guerbet alcohols based on fatty alcohols having 6 to 18,preferably 8 to 10, carbon atoms, esters of linear C₆-C₂₂-fatty acidswith linear or branched C₆-C₂₂-fatty alcohols or esters of branchedC₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols,such as, for example, myristyl myristate, myristyl palmitate, myristylstearate, myristyl isostearate, myristyl oleate, myristyl behenate,myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate,cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearylmyristate, stearyl palmitate, stearyl stearate, stearyl isostearate,stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate,isostearyl palmitate, isostearyl stearate, isostearyl isostearate,isostearyl oleate, isostearyl behenate, isostearyl oleate, oleylmyristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyloleate, oleyl behenate, oleyl erucate, behenyl myristate, behenylpalmitate, behenyl stearate, behenyl isostearate, behenyl oleate,behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate,erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate anderucyl erucate. Also suitable are esters of linear C₆-C₂₂-fatty acidswith branched alcohols, in particular 2-ethylhexanol, esters ofC₁₈-C₃₈-alkylhydroxy carboxylic acids with linear or branchedC₆-C₂₂-fatty alcohols, in particular Dioctyl Malate, esters of linearand/or branched fatty acids with polyhydric alcohols (such as, forexample, propylene glycol, dimerdiol or trimertriol) and/or Guerbetalcohols, triglycerides based on C₆-C₁₀-fatty acids, liquidmono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters ofC₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylicacids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acidswith linear or branched alcohols having 1 to 22 carbon atoms or polyolshaving 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils,branched primary alcohols, substituted cyclohexanes, linear and branchedC₆-C₂₂-fatty alcohol carbonates, such as, for example, DicaprylylCarbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcoholshaving 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acidwith linear and/or branched C₆-C₂₂-alcohols (e.g. Finsolv® TN), linearor branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22carbon atoms per alkyl group, such as, for example, dicaprylyl ether(Cetiol® OE), ring-opening products of epoxidized fatty acid esters withpolyols, silicone oils (cyclomethicones, silicone methicone grades,etc.) and/or aliphatic or naphthenic hydrocarbons, such as, for example,squalane, squalene or dialkylcyclohexanes.

Emulsifiers

Other surfactants may also be added to the preparations as emulsifiers,including for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0        to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto        C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15        carbon atoms in the alkyl group;    -   C_(12/18) fatty acid monoesters and diesters of addition        products of 1 to 30 mol ethylene oxide onto glycerol;    -   glycerol mono- and diesters and sorbitan mono- and diesters of        saturated and unsaturated fatty acids containing 6 to 22 carbon        atoms and ethylene oxide addition products thereof;    -   addition products of 15 to 60 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   polyol esters and, in particular, polyglycerol esters such as,        for example, polyglycerol polyricinoleate, polyglycerol        poly-12-hydroxystearate or polyglycerol dimerate isostearate.        Mixtures of compounds from several of these classes are also        suitable;    -   addition products of 2 to 15 mol ethylene oxide onto castor oil        and/or hydrogenated castor oil;    -   partial esters based on linear, branched, unsaturated or        saturated C_(6/22) fatty acids, ricinoleic acid and        12-hydroxystearic acid and glycerol, polyglycerol,        pentaerythritol, -dipentaerythritol, sugar alcohols (for example        sorbitol), alkyl glucosides (for example methyl glucoside, butyl        glucoside, lauryl glucoside) and polyglucosides (for example        cellulose);    -   mono-, di and trialkyl phosphates and mono-, di- and/or        tri-PEG-alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane/polyalkyl polyether copolymers and corresponding        derivatives;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl        glucose and polyols, preferably glycerol or polyglycerol,    -   polyalkylene glycols and    -   glycerol carbonate.

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols, glycerol mono- and diestersand sorbitan mono- and diesters of fatty acids or onto castor oil areknown commercially available products. They are homologue mixtures ofwhich the average degree of alkoxylation corresponds to the ratiobetween the quantities of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out. C_(12/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as lipid layer enhancers for cosmeticformulations. The preferred emulsifiers are described in more detail asfollows:

Partial glycerides. Typical examples of suitable partial glycerides arehydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,isostearic acid monoglyceride, isostearic acid diglyceride, oleic acidmonoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride,ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic aciddiglyceride, linolenic acid monoglyceride, linolenic acid diglyceride,erucic acid monoglyceride, erucic acid diglyceride, tartaric acidmonoglyceride, tartaric acid diglyceride, citric acid monoglyceride,citric acid diglyceride, malic acid monoglyceride, malic aciddiglyceride and technical mixtures thereof which may still contain smallquantities of triglyceride from the production process. Additionproducts of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto thepartial glycerides mentioned are also suitable.

Sorbitan esters. Suitable sorbitan esters are sorbitan monoisostearate,sorbitan sesquiisostearate, sorbitan diisostearate, sorbitantriisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitandioleate, sorbitan trioleate, sorbitan monoerucate, sorbitansesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitanmonoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate,sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitansesquihydroxystearate, sorbitan dihydroxystearate, sorbitantrihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate,sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate,sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate,sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate,sorbitan trimaleate and technical mixtures thereof. Addition products of1 to 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitanesters mentioned are also suitable.

Polyglycerol esters. Typical examples of suitable polyglycerol estersare Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH),Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate(Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate(Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Belling®), Polyglyceryl-4Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether(Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) andPolyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl DimerateIsostearate and mixtures thereof. Examples of other suitablepolyolesters are the mono-, di- and triesters of trimethylol propane orpentaerythritol with lauric acid, cocofatty acid, tallow fatty acid,palmitic acid, stearic acid, oleic acid, behenic acid and the likeoptionally reacted with 1 to 30 mol ethylene oxide.

Anionic emulsifiers. Typical anionic emulsifiers are aliphatic C₁₂₋₂₂fatty acids, such as palmitic acid, stearic acid or behenic acid forexample, and C₁₂₋₂₂ dicarboxylic acids, such as azelaic acid or sebacicacid for example.

Amphoteric emulsifiers. Other suitable emulsifiers are amphboteric orzwitterionic surfactants. Zwitterionic surfactants are surface-activecompounds which contain at least one quaternary ammonium group and atleast one carboxylate and one sulfonate group in the molecule.Particularly suitable zwitterionic surfactants are the so-calledbetaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, forexample cocoalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-cocoalkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Superfatting Agents and Consistency Factors

Superfatting agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

The consistency factors mainly used are fatty alcohols or hydroxyfattyalcohols containing 12 to 22 and preferably 16 to 18 carbon atoms andalso partial glycerides, fatty acids or hydroxyfatty acids. Acombination of these substances with alkyl oligoglucosides and/or fattyacid N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used.

Thickening Agents and Rheology Additives

Suitable thickeners are polymeric thickeners, such as Aerosil® types(hydrophilic silicas), polysaccharides, more especially xanthan gum,guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose andhydroxyethyl cellulose, also relatively high molecular weightpolyethylene glycol monoesters and diesters of fatty acids,polyacrylates (for example Carbopols® [Goodrich] or Synthalens®[Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone,surfactants such as, for example, ethoxylated fatty acid glycerides,esters of fatty acids with polyols, for example pentaerythritol ortrimethylol propane, narrow-range fatty alcohol ethoxylates andelectrolytes, such as sodium chloride and ammonium chloride.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides,quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, forexample, Luviquat® (BASF), condensation products of polyglycols andamines, quaternized collagen polypeptides such as, for example,Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau),quaternized wheat polypeptides, polyethyleneimine, cationic siliconepolymers such as, for example, amodimethicone, copolymers of adipic acidand dimethylaminohydroxypropyl diethylenetriamine (Cartaretine®,Sandoz), copolymers of acrylic acid with dimethyl diallyl ammoniumchloride (Merquat 550, Chemviron), polyaminopolyamides and crosslinkedwater-soluble polymers thereof, cationic chitin derivatives such as, forexample, quaternized chitosan, optionally in microcrystallinedistribution, condensation products of dihaloalkyls, for exampledibromobutane, with bis-dialkylamines, for examplebis-dimethylamino-1,3-propane, cationic guar gum such as, for example,Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 of Celanese, quaternizedammonium salt polymers such as, for example, Mirapol® A-15, Mirapol®AD-1, Mirapol® AZ-1 of Miranol and the various polyquaternium types (forexample 6, 7, 32 or 37) which can be found in the market under thetradenames Rheocare® CC or Ultragel® 300.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinylether/maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammoniumchloride/acrylate copolymers, octylacrylamide/methylmethacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinylacetate copolymers, vinyl pyrrolidone/dimethylaminoethylmethacrylate/vinyl caprolactam terpolymers and optionally derivatizedcellulose ethers and silicones.

Pearlizing Waxes

Suitable pearlising waxes are, for example, alkylene glycol esters,especially ethylene glycol distearate; fatty acid alkanolamides,especially cocofatty acid diethanolamide; partial glycerides, especiallystearic acid monoglyceride; esters of polybasic, optionallyhydroxy-substituted carboxylic acids with fatty alcohols containing 6 to22 carbon atoms, especially long-chain esters of tartaric acid; fattycompounds, such as for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates which contain in all atleast 24 carbon atoms, especially laurone and distearylether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid, ringopening products of olefin epoxides containing 12 to 22 carbon atomswith fatty alcohols containing 12 to 22 carbon atoms and/or polyolscontaining 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixturesthereof.

Silicones

Suitable silicone compounds are, for example, dimethyl polysiloxanes,methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.A detailed overview of suitable volatile silicones can be found in Toddet al. in Cosm. Toil. 91, 27 (1976).

Waxes and Stabilizers

Besides natural oils used, waxes may also be present in thepreparations, more especially natural waxes such as, for example,candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax,guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax,beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat,ceresine, ozocerite (earth wax), petrolatum, paraffin waxes andmicrowaxes; chemically modified waxes (hard waxes) such as, for example,montan ester waxes, sasol waxes, hydrogenated jojoba waxes and syntheticwaxes such as, for example, polyalkylene waxes and polyethylene glycolwaxes.

Metal salts of fatty acids such as, for example, magnesium, aluminiumand/or zinc stearate or ricinoleate may be used as stabilizers.

Primary Sun Protection Factors

Primary sun protection factors in the context of the invention are, forexample, organic substances (light filters) which are liquid orcrystalline at room temperature and which are capable of absorbingultraviolet radiation and of releasing the energy absorbed in the formof longer-wave radiation, for example heat.

The formulations according to the invention advantageously contain atleast one UV-A filter and/or at least one UV-B filter and/or a broadbandfilter and/or at least one inorganic pigment. Formulations according tothe invention preferably contain at least one UV-B filter or a broadbandfilter, more particularly preferably at least one UV-A filter and atleast one UV-B filter.

Preferred cosmetic compositions, preferably topical formulationsaccording to the present invention comprise one, two, three or more sunprotection factors selected from the group consistiung of 4-aminobenzoicacid and derivatives, salicylic acid derivatives, benzophenonederivatives, dibenzoylmethane derivatives, diphenyl acrylates,3-imidazol-4-yl acrylic acid and esters thereof, benzofuran derivatives,benzylidene malonate derivatives, polymeric UV absorbers containing oneor more organosilicon radicals, cinnamic acid derivatives, camphorderivatives, trianilino-s-triazine derivatives,2-hydroxyphenylbenzotriazole derivatives, phenylbenzimidazole sulfonicacid derivatives and salts thereof, anthranilic acid menthyl esters,benzotriazole derivativesand indole derivatives.

In addition, it is advantageous to combine compounds of formula (I) withactive ingredients which penetrate into the skin and protect the skincells from inside against sunlight-induced damage and reduce the levelof cutaneous matrix metalloproteases. Preferred respective ingredients,so called arylhydrocarbon receptor antagonists, are described in WO2007/128723, incorporated herein by reference. Preferred is2-benzylidene-5,6-dimethoxy-3,3-dimethylindan-1-one.

The UV filters cited below which can be used within the context of thepresent invention are preferred but naturally are not limiting.

UV filters which are preferably used are selected from the groupconsisting of

-   -   p-aminobenzoic acid    -   p-aminobenzoic acid ethyl ester (25 mol) ethoxylated (INCI name:        PEG-25 PABA)    -   p-dimethylaminobenzoic acid-2-ethylhexyl ester    -   p-aminobenzoic acid ethyl ester (2 mol) N-propoxylated    -   p-aminobenzoic acid glycerol ester    -   salicylic acid homomenthyl ester (homosalates) (Neo        Heliopan®HMS)    -   salicylic acid-2-ethylhexyl ester (Neo Heliopan®OS)    -   triethanolamine salicylate    -   4-isopropyl benzyl salicylate    -   anthranilic acid menthyl ester (Neo Heliopan®MA)    -   diisopropyl cinnamic acid ethyl ester    -   p-methoxycinnamic acid-2-ethylhexyl ester (Neo Heliopan®AV)    -   diisopropyl cinnamic acid methyl ester    -   p-methoxycinnamic acid isoamyl ester (Neo Heliopan®E 1000)    -   p-methoxycinnamic acid diethanolamine salt    -   p-methoxycinnamic acid isopropyl ester    -   2-phenylbenzimidazole sulfonic acid and salts (Neo        Heliopan®Hydro)    -   3-(4′-trimethylammonium) benzylidene bornan-2-one methyl sulfate    -   beta-imidazole-4(5)-acrylic acid (urocanic acid)    -   3-(4′-sulfo)benzylidene bornan-2-one and salts    -   3-(4′-methyl benzylidene)-D,L-camphor (Neo Heliopan®MBC)    -   3-benzylidene-D,L-camphor    -   N-[(2 and 4)-[2-(oxoborn-3-ylidene) methyl]benzyl] acrylamide        polymer    -   4,4′-[(6-[4-(1,1-dimethyl)aminocarbonyl)        phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic        acid-2-ethylhexyl ester) (Uvasorb®HEB)    -   benzylidene malonate polysiloxane (Parsol®SLX)    -   glyceryl ethylhexanoate dimethoxycinnamate    -   dipropylene glycol salicylate    -   tris(2-ethylhexyl)-4,4′,4″-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate        (=2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine)        (Uvinul® T150).

Broadband filters which are preferably combined with one or morecompounds of formula (I) in a preparation according to the presentinvention are selected from the group consisting of

-   -   2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)    -   ethyl-2-cyano-3,3′-diphenyl acrylate    -   2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB)    -   2-hydroxy-4-methoxybenzophenone-5-sulfonic acid    -   dihydroxy-4-methoxybenzophenone    -   2,4-dihydroxybenzophenone    -   tetrahydroxybenzophenone    -   2,2′-dihydroxy-4,4′-dimethoxybenzophenone    -   2-hydroxy-4-n-octoxybenzophenone    -   2-hydroxy-4-methoxy-4′-methyl benzophenone    -   sodium hydroxymethoxybenzophenone sulfonate    -   disodium-2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone    -   phenol,        2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)disiloxyanyl)        propyl) (Mexoryl®XL)    -   2,2′-methylene        bis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)        phenol) (Tinosorb® M)    -   2,4-bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3,5-triazine    -   2,4-bis-[{(4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine        (Tinosorb® S)    -   2,4-bis-[{(4-(3-sulfonato)-2-hydroxypropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine        sodium salt    -   2,4-bis-[{(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine    -   2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-[4-(2-methoxyethyl        carbonyl) phenylamino]-1,3,5-triazine    -   2,4-bis-[{4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy}phenyl]-6-[4-(2-ethylcarboxyl)        phenylamino]-1,3,5-triazine    -   2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(1-methylpyrrol-2-yl)-1,3,5-triazine    -   2,4-bis-[{4-tris-(trimethylsiloxysilylpropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine    -   2,4-bis-[{4-(2″-methylpropenyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine    -   2,4-bis-[{4-(1′,1′,1′,3′,5′,5′,5′-heptamethylsiloxy-2″-methylpropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine.

The compositions can comprise further typical detergent and cleansingcomposition ingredients such as UV-A filters filters which arepreferably combined with one or more compounds of formula (I) in apreparation according to the present invention are selected from thegroup consisting of

-   -   4-isopropyl dibenzoyl methane    -   terephthalylidene dibornane sulfonic acid and salts (Mexoryl®SX)    -   4-t-butyl-4′-methoxydibenzoyl methane (avobenzone)/(Neo        Heliopan®357)    -   phenylene bis-benzimidazyl tetrasulfonic acid disodium salt (Neo        Heliopan®AP)    -   2,2′-(1,4-phenylene)-bis-(1H-benzimidazole-4,6-disulfonic acid),        monosodium salt    -   2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester        (Uvinul A Plus)    -   indanylidene compounds in accordance with DE 100 55 940 A1 (=WO        2002 038537 A1)

The compositions can comprise further typical detergent and cleansingcomposition ingredients such as UV filters which are more preferablycombined with one or more compounds of formula (I) in a preparationaccording to the present invention are selected from the groupconsisting of

-   -   p-aminobenzoic acid    -   3-(4′-trimethylammonium) benzylidene bornan-2-one methyl sulfate    -   salicylic acid homomenthyl ester (Neo Heliopan®HMS)    -   2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB)    -   2-phenylbenzimidazole sulfonic acid (Neo Heliopan®Hydro)    -   terephthalylidene dibornane sulfonic acid and salts (Mexoryl®SX)    -   4-tert-butyl-4′-methoxydibenzoyl methane (Neo Heliopan®357)    -   3-(4′-sulfo)benzylidene bornan-2-one and salts    -   2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)    -   N-[(2 and 4)-[2-(oxoborn-3-ylidene) methyl]benzyl] acrylamide        polymer    -   p-methoxycinnamic acid-2-ethylhexyl ester (Neo Heliopan®AV)    -   p-aminobenzoic acid ethyl ester (25 mol) ethoxylated (INCI name:        PEG-25 PABA)    -   p-methoxycinnamic acid isoamyl ester (Neo Heliopan®E1000)    -   2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine        (Uvinul®T150)    -   phenol,        2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)disiloxyanyl)        propyl) (Mexoryl®XL)    -   4,4′-[(6-[4-(1,1-dimethyl)aminocarbonyl)        phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic        acid-2-ethylhexyl ester) (Uvasorb HEB)    -   3-(4′-methyl benzylidene)-D,L-camphor (Neo Heliopan®MBC)    -   3-benzylidene camphor    -   salicylic acid-2-ethylhexyl ester (Neo Heliopan®OS)    -   4-dimethylaminobenzoic acid-2-ethylhexyl ester (Padimate O)    -   hydroxy-4-methoxybenzophenone-5-sulfonic acid and Na salt    -   2,2′-methylene        bis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)        phenol) (Tinosorb®M)    -   phenylene bis-benzimidazyl tetrasulfonic acid disodium salt (Neo        Heliopan®AP)    -   2,4-bis-[{(4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine        (Tinosorb®S)    -   benzylidene malonate polysiloxane (Parsol®SLX)    -   menthyl anthranilate (Neo Heliopan®MA)    -   2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester        (Uvinul® A Plus)    -   indanylidene compounds in accordance with DE 100 55 940 (=WO        02/38537).

Advantageous primary and also secondary sun protection factors arementioned in WO 2005 123101 A1. Advantageously, these preparationscontain at least one UVA filter and/or at least one UVB filter and/or atleast one inorganic pigment. The preparations may be present here invarious forms such as are conventionally used for sun protectionpreparations. Thus, they may be in form of a solution, an emulsion ofthe water-in-oil type (W/O) or of the oil-in-water type (O/W) or amultiple emulsion, for example of the water-in-oil-in-water type(W/O/W), a gel, a hydrodispersion, a solid stick or else an aerosol.

In a further preferred embodiment a formulation according to theinvention contains a total amount of sunscreen agents, i.e. inparticular UV filters and/or inorganic pigments (UV filtering pigments)so that the formulation according to the invention has a lightprotection factor of greater than or equal to 2 (preferably greater thanor equal to 5). Such formulations according to the invention areparticularly suitable for protecting the skin and hair.

Secondary Sun Protection Factors

Besides the groups of primary sun protection factors mentioned above,secondary sun protection factors of the antioxidant type may also beused. Secondary sun protection factors of the antioxidant type interruptthe photochemical reaction chain which is initiated when UV rayspenetrate into the skin. Typical examples are amino acids (for exampleglycine, histidine, tyrosine, tryptophane) and derivatives thereof,imidazoles (for example urocanic acid) and derivatives thereof,peptides, such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (for example anserine), carotinoids, carotenes (forexample alpha-carotene, beta-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, liponic acid andderivatives thereof (for example dihydroliponic acid), aurothioglucose,propylthiouracil and other thiols (for example thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,alpha-linoleyl, cholesteryl and glyceryl esters thereof) and theirsalts, dilaurylthiodipropionate, distearylthiodipropionate,thiodipropionic acid and derivatives thereof (esters, ethers, peptides,lipids, nucleotides, nucleosides and salts) and sulfoximine compounds(for example butionine sulfoximines, homocysteine sulfoximine, butioninesulfones, penta-, hexa- and hepta-thionine sulfoximine) in very smallcompatible dosages, also (metal) chelators (for examplealpha-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine),alpha-hydroxy acids (for example citric acid, lactic acid, malic acid),humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTAand derivatives thereof, unsaturated fatty acids and derivatives thereof(for example linoleic acid, oleic acid), folic acid and derivativesthereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives thereof (for example ascorbyl palmitate, Mg ascorbylphosphate, ascorbyl acetate), tocopherols and derivatives (for examplevitamin E acetate), vitamin A and derivatives (vitamin A palmitate) andconiferyl benzoate of benzoin resin, rutinic acid and derivativesthereof, glycosyl rutin, ferulic acid, furfurylidene glucitol,carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiacresin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uricacid and derivatives thereof, mannose and derivatives thereof,superoxide dismutase, titanium dioxide (for example dispersions inethanol), zinc and derivatives thereof (for example ZnO, ZnSO₄),selenium and derivatives thereof (for example selenium methionine),stilbenes and derivatives thereof (for example stilbene oxide,trans-stilbene oxide) and derivatives of these active substancessuitable for the purposes of the invention (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids).

Advantageous inorganic secondary light protection pigments are finelydispersed metal oxides and metal salts which are also mentioned in WO2005 123101 A1. The total quantity of inorganic pigments, in particularhydrophobic inorganic micro-pigments in the finished cosmeticpreparation according to the present invention is advantageously from0.1 to 30% by weight, preferably 0.5 to 10.0% by weight, in each casebased on the total weight of the preparation.

Also preferred are particulate UV filters or inorganic pigments, whichcan optionally be hydrophobed, can be used, such as the oxides oftitanium (TiO₂), zinc (ZnO), iron (Fe₂O₃), zirconium (ZrO₂), silicon(SiO₂), manganese (e.g. MnO), aluminium (Al₂O₃), cerium (e.g. Ce₂O₃)and/or mixtures thereof.

Actives Modulating Skin and/or Hair Pigmentation

Preferred active ingredients for skin and/or hair lightening areselected from the group consisting of: kojic acid(5-hydroxy-2-hydroxymethyl-4-pyranone), kojic acid derivatives,preferably kojic acid dipalmitate, arbutin, ascorbic acid, ascorbic acidderivatives, preferably magnesium ascorbyl phosphate, hydroquinone,hydroquinone derivatives, resorcinol, resorcinol derivatives, preferably4-alkylresorcinols and 4-(1-phenylethyl)1,3-dihydroxybenzene(phenylethyl resorcinol), cyclohexylcarbamates (preferably one or morecyclohexyl carbamates disclosed in WO 2010/122178 and WO 2010/097480),sulfur-containing molecules, preferably glutathione or cysteine,alpha-hydroxy acids (preferably citric acid, lactic acid, malic acid),salts and esters thereof, N-acetyl tyrosine and derivatives, undecenoylphenylalanine, gluconic acid, chromone derivatives, preferably aloesin,flavonoids, 1-aminoethyl phosphinic acid, thiourea derivatives, ellagicacid, nicotinamide (niacin-amide), zinc salts, preferably zinc chlorideor zinc gluconate, thujaplicin and derivatives, triterpenes, preferablymaslinic acid, sterols, preferably ergosterol, benzofuranones,preferably senkyunolide, vinyl guiacol, ethyl guiacol, dionic acids,preferably octodecene dionic acid and/or azelaic acid, inhibitors ofnitrogen oxide synthesis, preferably L-nitroarginine and derivativesthereof, 2,7-dinitroindazole or thiocitrulline, metal chelators(preferably alpha-hydroxy fatty acids, phytic acid, humic acid, bileacid, bile extracts, EDTA, EGTA and derivatives thereof), retinoids, soymilk and extract, serine protease inhibitors or lipoic acid or othersynthetic or natural active ingredients for skin and hair lightening,the latter preferably used in the form of an extract from plants,preferably bearberry extract, rice extract, papaya extract, turmericextract, mulberry extract, bengkoang extract, nutgrass extract,liquorice root extract or constituents concentrated or isolatedtherefrom, preferably glabridin or licochalcone A, artocarpus extract,extract of rumex and ramulus species, extracts of pine species (pinus),extracts of vitis species or stilbene derivatives isolated orconcentrated therefrom, saxifrage extract, scutelleria extract, grapeextract and/or microalgae extract, in particular Tetraselmis suecicaExtract.

Preferred skin lighteners as component (b) are kojic acid andphenylethyl resorcinol as tyrosinase inhibitors, beta- andalpha-arbutin, hydroquinone, nicotinamide, dioic acid, Mg ascorbylphosphate and vitamin C and its derivatives, mulberry extract, Bengkoangextract, papaya extract, turmeric extract, nutgrass extract, licoriceextract (containing glycyrrhizin), alpha-hydroxy-acids,4-alkylresorcinols, 4-hydroxyanisole. These skin lighteners arepreferred due to their very good activity, in particular in combinationwith sclareolide according to the present invention. In addition, saidpreferred skin lighteners are readily available.

Advantageous skin and hair tanning active ingredients in this respectare substrates or substrate analogues of tyrosinase such as L-tyrosine,N-acetyl tyrosine, L-DOPA or L-dihydroxyphenylalanine, xanthinealkaloids such as caffeine, theobromine and theophyl-line andderivatives thereof, proopiomelanocortin peptides such as ACTH,alpha-MSH, peptide analogues thereof and other substances which bind tothe melanocortin receptor, peptides such as Val-Gly-Val-Ala-Pro-Gly,Lys-Ile-Gly-Arg-Lys or Leu-Ile-Gly-Lys, purines, pyrimidines, folicacid, copper salts such as copper gluconate, chloride or pyrrolidonate,1,3,4-oxadiazole-2-thiols such as5-pyrazin-2-yl-1,3,4-oxadiazole-2-thiol, curcumin, zinc diglycinate(Zn(Gly)2), manganese(II) bicarbonate complexes (“pseudocat-alases”) asdescribed for example in EP 0 584 178, tetrasubstituted cyclohexenederiva-tives as described for example in WO 2005/032501, isoprenoids asdescribed in WO 2005/102252 and in WO 2006/010661, melanin derivativessuch as Melasyn-100 and MelanZe, diacyl glycerols, aliphatic or cyclicdiols, psoralens, prostaglandins and ana-logues thereof, activators ofadenylate cyclase and compounds which activate the transfer ofmelanosomes to keratinocytes such as serine proteases or agonists of thePAR-2 receptor, extracts of plants and plant parts of the chrysanthemumspecies, san-guisorba species, walnut extracts, urucum extracts, rhubarbextracts, microalgae extracts, in particular Isochrysis galbana,trehalose, erythru-lose and dihydroxyacetone. Flavonoids which bringabout skin and hair tinting or brown-ing (e.g. quercetin, rhamnetin,kaempferol, fisetin, genistein, daidzein, chrysin and api-genin,epicatechin, diosmin and diosmetin, morin, quercitrin, naringenin,hesperidin, phloridzin and phloretin) can also be used.

The amount of the aforementioned examples of additional activeingredients for the modulation of skin and hair pigmentation (one ormore compounds) in the products according to the invention is thenpreferably 0.00001 to 30 wt. %, preferably 0.0001 to 20 wt. %,particularly preferably 0.001 to 5 wt. %, based on the total weight ofthe preparation.

Anti-Ageing Actives

In the context of the invention, anti-ageing or biogenic agents are, forexample antioxidants, matrix-metalloproteinase inhibitors (MMPI), skinmoisturizing agents, glycosaminglycan stimulators, anti-inflammatoryagents, TRPV1 antagonists and plant extracts.

Antioxidants. Suitable antioxidants encompass amino acids (preferablyglycine, histidine, tyrosine, tryptophane) and derivatives thereof,imidazoles (preferably urocanic acid) and derivatives thereof, peptides,preferably D,L-carnosine, D-carnosine, L-carnosine and derivativesthereof (preferably anserine), carnitine, creatine, matrikine peptides(preferably lysyl-threonyl-threonyl-lysyl-serine) and palmitoylatedpentapeptides, carotenoids, carotenes (preferably alpha-carotene,beta-carotene, lycopene) and derivatives thereof, lipoic acid andderivatives thereof (preferably dihydrolipoic acid), aurothioglucose,propyl thiouracil and other thiols (preferably thioredoxine,glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl,methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,gamma-linoleyl, cholesteryl, glyceryl and oligoglyceryl esters thereof)and salts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof(preferably esters, ethers, peptides, lipids, nucleotides, nucleosidesand salts) and sulfoximine compounds (preferably buthioninesulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-,hexa-, heptathionine sulfoximine) in very small tolerated doses (e.g.pmol to μmol/kg), also (metal) chelators (preferably alpha-hydroxy fattyacids, palmitic acid, phytic acid, lactoferrin, alpha-hydroxy acids(preferably citric acid, lactic acid, malic acid), humic acid, bileacid, bile extracts, tannins, bilirubin, biliverdin, EDTA, EGTA andderivatives thereof), unsaturated fatty acids and derivatives thereof(preferably gamma-linolenic acid, linoleic acid, oleic acid), folic acidand derivatives thereof, ubiquinone and derivatives thereof, ubiquinoland derivatives thereof, vitamin C and derivatives (preferably ascorbylpalmitate, Mg ascorbyl phosphate, ascorbyl acetate, ascorbyl glucoside),tocopherols and derivatives (preferably vitamin E acetate), vitamin Aand derivatives (vitamin A palmitate) and coniferyl benzoate of benzoicresin, rutinic acid and derivatives thereof, flavonoids and glycosylatedprecursors thereof, in particular quercetin and derivatives thereof,preferably alpha-glucosyl rutin, rosmarinic acid, carnosol, carnosolicacid, resveratrol, caffeic acid and derivatives thereof, sinapic acidand derivatives thereof, ferulic acid and derivatives thereof,curcuminoids, chlorogenic acid and derivatives thereof, retinoids,preferably retinyl palmitate, retinol or tretinoin, ursolic acid,levulinic acid, butyl hydroxytoluene, butyl hydroxyanisole,nordihydroguaiac acid, nordihydroguaiaretic acid,trihydroxybutyrophenone, uric acid and derivatives thereof, mannose andderivatives thereof, zinc and derivatives thereof (preferably ZnO,ZnSO₄), selenium and derivatives thereof (preferably seleniummethionine), superoxide dismutase, stilbenes and derivatives thereof(preferably stilbene oxide, trans-stilbene oxide) and the derivatives(salts, esters, ethers, sugars, nucleotides, nucleosides, peptides andlipids) of these cited active ingredients which are suitable accordingto the invention or extracts or fractions of plants having anantioxidant effect, preferably green tea, rooibos, honeybush, grape,rosemary, sage, melissa, thyme, lavender, olive, oats, cocoa, ginkgo,ginseng, liquorice, honeysuckle, sophora, pueraria, pinus, citrus,Phyllanthus emblica or St. John's wort, grape seeds, wheat germ,Phyllanthus emblica, coenzymes, preferably coenzyme Q10, plastoquinoneand menaquinone. Preferred antioxidants are selected from the groupconsisting of vitamin A and derivatives, vitamin C and derivatives,tocopherol and derivatives, preferably tocopheryl acetate, andubiquinone.

If vitamin E and/or derivatives thereof are used as the antioxidant(s),it is advantageous to choose their concentrations from the range fromabout 0.001 to about 10% b.w. based on the total weight of theformulation. If vitamin A or vitamin A derivatives or carotenes orderivatives thereof are used as the antioxidant(s), it is advantageousto choose their concentrations from the range from about 0.001 to aout10% b.w. based on the total weight of the formulation.

Matrix-Metalloproteinase inhibitors (MMPI). Preferred compositionscomprise matrix-metalloproteinase inhibitors, especially thoseinhibiting matrix-metalloproteinases enzymatically cleaving collagen,selected from the group consisting of: ursolic acid, retinyl palmitate,propyl gallate, precocenes,6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran,3,4-dihydro-6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran,benzamidine hydrochloride, the cysteine proteinase inhibitorsN-ethylmalemide and epsilon-amino-n-caproic acid of the serinproteaseinhibitors: phenylmethylsufonylfluoride, collhibin (company Pentapharm;INCI: hydrolysed rice protein), oenotherol (company Soliance; INCI:propylene glycol, aqua, Oenothera biennis root extract, ellagic acid andellagitannins, for example from pomegranate), phosphoramidonehinokitiol, EDTA, galardin, EquiStat (company Collaborative Group; applefruit extract, soya seed extract, ursolic acid, soya isoflavones andsoya proteins), sage extracts, MDI (company Atrium; INCI:glycosaminoglycans), fermiskin (company Silab/Mawi; INCI: water andlentinus edodes extract), actimp 1.9.3 (company Expanscience/Rahn; INCI:hydrolysed lupine protein), lipobelle soyaglycone (company Mibelle;INCI: alcohol, polysorbate 80, lecithin and soy isoflavones), extractsfrom green and black tea and further plant extracts, which are listed inWO 02 069992 A1 (see tables 1-12 there, incorporated herein byreference), proteins or glycoproteins from soya, hydrolysed proteinsfrom rice, pea or lupine, plant extracts which inhibit MMPs, preferablyextracts from shitake mushrooms, extracts from the leaves of theRosaceae family, sub-family Rosoideae, quite particularly extracts ofblackberry leaf (preferably as described in WO 2005 123101 A1,incorporated herein by reference) as e.g. SymMatrix (company Symrise,INCI: Maltodextrin, Rubus Fruticosus (Blackberry) Leaf Extract).Preferred actives of are selected from the group consisting of retinylpalmitate, ursolic acid, extracts from the leaves of the Rosaceaefamily, sub-family Rosoideae, genistein and daidzein.

Skin-moisturizing agents. Preferred skin moisturizing agents areselected from the group consisting of alkane diols or alkane triolscomprising 3 to 12 carbon atoms, preferably C₃-C₁₀-alkane diols andC₃-C₁₀-alkane triols. More preferably the skin moisturizing agents areselected from the group consisting of: glycerol, 1,2-propylene glycol,1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol,1,2-hexanediol, 1,2-octanediol and 1,2-decanediol.

Glycosaminoglycan stimulators. Preferred compositions comprisesubstances stimulating the synthesis of glycosaminoglycans selected fromthe group consisting of hyaluronic acid and derivatives or salts,Subliskin (Sederma, INCI: Sinorhizobium Meliloti Ferment Filtrate, CetylHydroxyethylcellulose, Lecithin), Hyalufix (BASF, INCI: Water, ButyleneGlycol, Alpinia galanga leaf extract, Xanthan Gum, Caprylic/CapricTriglyceride), Stimulhyal (Soliance, INCI: Calcium ketogluconate),Syn-Glycan (DSM, INCI: Tetradecyl Aminobutyroylvalylaminobutyric UreaTrifluoroacetate, Glycerin, Magnesium chloride), Kalpariane (BiotechMarine), DC Upregulex (Distinctive Cosmetic Ingredients, INCI: Water,Butylene Glycol, Phospholipids, Hydrolyzed Sericin), glucosamine,N-acetyl glucosamine, retinoids, preferably retinol and vitamin A,Arctium lappa fruit extract, Eriobotrya japonica extract, Genkwanin,N-Methyl-L-serine, (−)-alpha-bisabolol or synthetic alpha-bisabolol suchas e.g. Dragosantol and Dragosantol 100 from Symrise, oat glucan,Echinacea purpurea extract and soy protein hydrolysate. Preferredactives are selected from the group consisting of hyaluronic acid andderivatives or salts, retinol and derivatives, (−)-alpha-bisabolol orsynthetic alpha-bisabolol such as e.g. Dragosantol and Dragosantol 100from Symrise, oat glucan, Echinacea purpurea extract, SinorhizobiumMeliloti Ferment Filtrate, Calcium ketogluconate, Alpinia galanga leafextract and tetradecyl aminobutyroylvalylaminobutyric ureatrifluoroacetate.

Anti-inflammatory agents. The compositions may also containanti-inflammatory and/or redness and/or itch ameliorating ingredients,in particular steroidal substances of the corticosteroid type selectedfrom the group consisting of hydrocortisone, dexamethasone,dexamethasone phosphate, methyl prednisolone or cortisone, areadvantageously used as anti-inflammatory active ingredients or activeingredients to relieve reddening and itching, the list of which can beextended by the addition of other steroidal anti-inflammatories.Non-steroidal anti-inflammatories can also be used. Examples which canbe cited here are oxicams such as piroxicam or tenoxicam; salicylatessuch as aspirin, disalcid, solprin or fendosal; acetic acid derivativessuch as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin orclindanac; fenamates such as mefenamic, meclofenamic, flufenamic orniflumic; propionic acid derivatives such as ibuprofen, naproxen,benoxaprofen or pyrazoles such as phenylbutazone, oxyphenylbutazone,febrazone or azapropazone. Anthranilic acid derivatives, in particularavenanthramides described in WO 2004 047833 A1, are preferred anti-itchingredients in a composition according to the present invention.

Also useful are natural or naturally occurring anti-inflammatorymixtures of substances or mixtures of substances that alleviatereddening and/or itching, in particular extracts or fractions fromcamomile, Aloe vera, Commiphora species, Rubia species, willow,willow-herb, oats, calendula, arnica, St John's wort, honeysuckle,rosemary, Passiflora incarnata, witch hazel, ginger or Echinacea;preferably selected from the group consisting of extracts or fractionsfrom camomile, Aloe vera, oats, calendula, arnica, honeysuckle,rosemary, witch hazel, ginger or Echinacea, and/or pure substances,preferably alpha-bisabolol, apigenin, apigenin-7-glucoside, gingerols,shogaols, gingerdiols, dehydrogingerdiones, paradols, natural ornaturally occuring avenanthramides, preferably tranilast, avenanthramideA, avenanthramide B, avenanthramide C, non-natural or non-naturallyoccuring avenanthramides, preferably dihydroavenanthramide D,dihydroavenanthramide E, avenan-thramide D, avenan-thramide E,avenanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridinand licochalcone A; preferably selected from the group consisting ofalpha-bisabolol, natural avenanthramides, non-natural avenanthramides,preferably dihydroavenanthramide D (as described in WO 2004 047833 A1),boswellic acid, phytosterols, glycyrrhizin, and licochalcone A, and/orallantoin, panthenol, lanolin, (pseudo-)ceramides [preferably Ceramide2, hydroxypropyl bispalmitamide MEA, cetyloxypropyl glycerylmethoxypropyl myristamide, N-(1-hexadecanoyl)-4-hydroxy-L-proline(1-hexadecyl) ester, hydroxyethyl palmityl oxyhydroxypropylpalmitamide], glycosphingolipids, phytosterols, chitosan, mannose,lactose and β-glucans, in particular 1,3-1,4-β-glucan from oats.

When bisabolol is used in the context of the present invention it can beof natural or synthetic origin, and is preferably “alpha-bisabolol”.Preferably, the bisabolol used is synthetically prepared or natural(−)-alpha-bisabolol and/or synthetic mixed-isomer alpha-bisabolol. Ifnatural (−)-alpha-bisabolol is used, this can also be employed as aconstituent of an essential oil or of a plant extract or of a fractionthereof, for example as a constituent of (fractions of) oil or extractsof camomile or of Vanillosmopsis (in particular Vanillosmopsiserythropappa or Vanillosmopsis arborea). Synthetic alpha-bisabolol isobtainable, for example, under the name “Dragosantol” from Symrise.

In case ginger extract is used in the context of the present invention,preferably extracts of the fresh or dried ginger root are used which areprepared by extraction with methanol, ethanol, iso-propanol, acetone,ethyl acetate, carbon dioxide (CO2), hexane, methylene chloride,chloroform or other solvents or solvent mixtures of comparable polarity.The extracts are characterized by the presence of active skinirritation-reducing amounts of constituents such as e.g. gingerols,shogaols, gingerdiols, dehydrogingerdiones and/or paradols.

TRPV1 antagonists. Suitable compounds which reduce the hypersensitivityof skin nerves based on their action as TRPV1 antagonists, encompasse.g. trans-4-tert-butyl cyclohexanol as described in WO 2009 087242 A1,or indirect modulators of TRPV1 by an activation of the μ-receptor, e.g.acetyl tetrapeptide-15, are preferred.

Desquamating agents. The compositions may also contain desquamatingagents (component b5) in amounts of about 0.1 to about 30% b.w.preferably about 0.5 to about 15% b.w., particularly preferably about 1to about 10% b.w. based on the total weight of the preparation. Theexpression “desquamating agent” is understood to mean any compoundcapable of acting:

-   -   either directly on desquamation by promoting exfoliation, such        as β-hydroxy acids, in particular salicylic acid and its        derivatives (including 5-n-octanoylsalicylic acid); α-hydroxy        acids, such as glycolic, citric, lactic, tartaric, malic or        mandelic acids; urea; gentisic acid; oligofucoses; cinnamic        acid; extract of Sophora japonica; resveratrol and some        derivatives of jasmonic acid;    -   or on the enzymes involved in the desquamation or the        degradation of the corneodesmosomes, glycosidases, stratum        corneum chymotryptic enzyme (SCCE) or other proteases (trypsin,        chymotrypsin-like). There may be mentioned agents chelating        inorganic salts: EDTA; N-acyl-N,N′,N′-ethylenediaminetriacetic        acid; aminosulphonic compounds and in particular        (N-2-hydroxyethylpiperazine-N-2-ethane)sulphonic acid (HEPES);        derivatives of 2-oxothiazolidine-4-carboxylic acid        (procysteine); derivatives of alpha-amino acids of the glycine        type (as described in EP-0 852 949, and sodium methylglycine        diacetate marketed by BASF under the trade name TRILON M);        honey; sugar derivatives such as O-octanoyl-6-D-maltose and        N-acetylglucosamine; chestnut extracts such as those marketed by        the company SILAB under the name Recoverine®, prickly pear        extracts such as those marketed under the name Exfolactive® by        the company SILAB, or Phytosphingosine SLC® (phytosphingosine        grafted with a salicylic acid) marketed by the company Degussa.

Desquamating agents suitable for the invention may be chosen inparticular from the group comprising sulphonic acids, calcium chelators,a-hydroxy acids such as glycolic, citric, lactic, tartaric, malic ormandelic acids; ascorbic acid and its derivatives such as ascorbylglucoside and magnesium ascorbyl phosphate; nicotinamide; urea;(N-2-hydroxyethylpiperazine-N-2-ethane)sulphonic acid (HEPES), β-hydroxyacids such as salicylic acid and its derivatives, retinoids such asretinol and its esters, retinal, retinoic acid and its derivatives,those described in the documents FR 2570377 A1, EP 0199636 A1, EP0325540 A1, EP 0402072 A1, chestnut or prickly pear extracts, inparticular marketed by SILAB; reducing compounds such as cysteine orcysteine precursors.

Desquamating agents which can be used are also nicotinic acid and itsesters and nicotinamide, also called vitamin B3 or vitamin PP, andascorbic acid and its precursors, as described in particular inapplication EP 1529522 A1.

Anti-cellulite agents. Anti-cellulite agents and lipolytic agents arepreferably selected from the group consisting of those described in WO2007/077541, and beta-adrenergic receptor agonists such as synephrineand its derivatives, and cyclohexyl carbamates described in WO2010/097479. Agents enhancing or boosting the activity of anti-celluliteagents, in particular agents which stimulate and/or depolarise C nervefibres, are preferably selected from the group consisting of capsaicinand derivatives thereof, vanillyl-nonylamid and derivatives thereof,L-carnitine, coenzym A, isoflavonoides, soy extracts, ananas extract andconjugated linoleic acid.

Fat enhancing agents. Formulations and products according to the presentinvention may also comprise one or more fat enhancing and/or adipogenicagents as well as agents enhancing or boosting the activity of fatenhancing agents. A fat enhancing agent is for examplehydroxymethoxyphenyl propylmethylmethoxybenzofuran (trade name:)Sym3D®).

Hair Growth Activators or Inhibitors

Formulations and products according to the present invention may alsocomprise one or more hair growth activators, i.e. agents to stimulatehair growth. Hair growth activators are preferably selected from thegroup consisting of pyrimidine derivatives such as2,4-diaminopyrimidine-3-oxide (Aminexil),2,4-diamino-6-piperidinopyrimidine-3-oxide (Minoxidil) and derivativesthereof, 6-amino-1,2-dihydro-1-hydroxy-2-imino-4-piperidinopyrimidineand its derivatives, xanthine alkaloids such as caffeine, theobromineand theophylline and derivatives thereof, quercetin and derivatives,dihydroquercetin (taxifolin) and derivatives, potassium channel openers,antiandrogenic agents, synthetic or natural 5-reductase inhibitors,nicotinic acid esters such as tocopheryl nicotinate, benzyl nicotinateand C1-C6 alkyl nicotinate, proteins such as for example the tripeptideLys-Pro-Val, diphencypren, hormons, finasteride, dutasteride, flutamide,bicalutamide, pregnane derivatives, progesterone and its derivatives,cyproterone acetate, spironolactone and other diuretics, calcineurininhibitors such as FK506 (Tacrolimus, Fujimycin) and its derivatives,Cyclosporin A and derivatives thereof, zinc and zinc salts, polyphenols,procyanidins, proanthocyanidins, phytosterols such as for examplebeta-sitosterol, biotin, eugenol, (±)-beta-citronellol, panthenol,glycogen for example from mussels, extracts from microorganisms, algae,plants and plant parts of for example the genera dandelion (Leontodon orTaraxacum), Orthosiphon, Vitex, Coffea, Paullinia, Theobroma, Asiasarum,Cucurbita or Styphnolobium, Serenoa repens (saw palmetto), Sophoraflavescens, Pygeum africanum, Panicum miliaceum, Cimicifuga racemosa,Glycine max, Eugenia caryophyllata, Cotinus coggygria, Hibiscusrosa-sinensis, Camellia sinensis, Ilex paraguariensis, Isochrysisgalbana, licorice, grape, apple, barley or hops or/nd hydrolysates fromrice or wheat.

Alternatively, formulations and products according to the presentinvention may comprise one or more hair growth inhibitors (as describedabove), i.e. agents to reduce or prevent hair growth. Hair growthinhibitors are preferably selected from the group consisting of activin,activin derivatives or activin agonists, ornithine decarboxylaseinhibitors such as alpha-difluoromethylornithine or pentacyclictriterpenes like for example ursolic acid, betulin, betulinic acid,oleanolic acid and derivatives thereof, 5alpha-reductase inhibitors,androgen receptor antagonists, S-adenosylmethionine decarboxylaseinhibitors, gamma-glutamyl transpeptidase inhibitors, transglutaminaseinhibitors, soybean-derived serine protease inhibitors, extracts frommicroorganisms, algae, different microalgae or plants and plant parts offor example the families Leguminosae, Solanaceae, Graminae,Asclepiadaceae or Cucurbitaceae, the genera Chondrus, Gloiopeltis,Ceramium, Durvillea, Glycine max, Sanguisorba officinalis, Calendulaofficinalis, Hamamelis virginiana, Arnica montana, Salix alba, Hypericumperforatum or Gymnema sylvestre.

Physiological Cooling Agents

The compositions may also contain one or more substances with aphysiological cooling effect (cooling agents), which are preferablyselected here from the following list: menthol and menthol derivatives(for example L-menthol, D-menthol, racemic menthol, isomenthol,neoisomenthol, neomenthol) menthylethers (for example(l-menthoxy)-1,2-propandiol, (1-menthoxy)-2-methyl-1,2-propandiol,1-menthyl-methylether), menthylesters (for example menthylformiate,menthylacetate, menthylisobutyrate, menthyllactates,L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)acetate,menthyl-(2-methoxyethoxy)acetate, menthylpyroglutamate),menthylcarbonates (for example menthylpropyleneglycolcarbonate,menthylethyleneglycolcarbonate, menthylglycerolcarbonate or mixturesthereof), the semi-esters of menthols with a dicarboxylic acid orderivatives thereof (for example mono-menthylsuccinate,mono-menthylglutarate, mono-menthylmalonate, O-menthyl succinic acidester-N,N-(dimethyl)amide, O-menthyl succinic acid ester amide),menthanecarboxylic acid amides (in this case preferablymenthanecarboxylic acid-N-ethylamide [WS3] orN^(α)-(menthanecarbonyl)glycinethylester [WS5], as described in U.S.Pat. No. 4,150,052, menthanecarboxylic acid-N-(4-cyanophenyl)amide ormenthane-carboxylic acid-N-(4-cyanomethylphenyl)amide as described in WO2005 049553 A1, methanecarboxylic acid-N-(alkoxyalkyl)amides), menthoneand menthone derivatives (for example L-menthone glycerol ketal),2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (for example2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegolor its esters (l-(−)-isopulegol, l-(−)-isopulegolacetate), menthanederivatives (for example p-menthane-3,8-diol), cubebol or synthetic ornatural mixtures, containing cubebol, pyrrolidone derivatives ofcycloalkyldione derivatives (for example3-methyl-2(1-pyrrolidinyl)-2-cyclopentene-1-one) ortetrahydropyrimidine-2-one (for example iciline or related compounds, asdescribed in WO 2004/026840), further carboxamides (for exampleN-(2-(pyridin-2-yl)ethyl)-3-p-menthanecarboxamide or related compounds),(1R,2S,5R)—N-(4-Methoxyphenyl)-5-methyl-2-(1-isopropyl)cyclohexane-carboxamide[WS12], oxamates (preferably those described in EP 2033688 A2).

Anti-Inflammatory Agents

Suitable anti-inflammatory agents may be selected from the group formedby:

-   (i) steroidal anti-inflammatory substances of the corticosteroid    type, in particular hydrocortisone, hydrocortisone derivatives such    as hydrocortisone 17-butyrate, dexamethasone, dexamethasone    phosphate, methylprednisolone or cortisone,-   (ii) non-steroidal anti-inflammatory substances, in particular    oxicams such as piroxicam or tenoxicam, salicylates such as aspirin,    disalcid, solprin or fendosal, acetic acid derivatives such as    diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or    clindanac, fenamates such as mefenamic, meclofenamic, flufenamic or    niflumic, propionic acid derivatives such as ibuprofen, naproxen or    benoxaprofen, pyrazoles such as phenylbutazone, oxyphenylbutazone,    febrazone or azapropazone,-   (iii) natural or naturally occuring anti-inflammatory substances or    substances that alleviate reddening and/or itching, in particular    extracts or fractions from camomile, Aloe vera, Commiphora species,    Rubia species, willow, willow-herb, oats, calendula, arnica, St    John's wort, honeysuckle, rosemary, Passiflora incarnata, witch    hazel, ginger or Echinacea, or single active compounds thereof,-   (iv) histamine receptor antagonists, serine protease inhibitors    (e.g. of Soy extracts), TRPV1 antagonists (e.g.    4-t-Butylcyclohexanol), NK1 antagonists (e.g. Aprepitant,    Hydroxyphenyl Propamidobenzoic Acid), cannabinoid receptor agonists    (e.g. Palmitoyl Ethanolamine) and TRPV3 antagonists.

Physiological Cooling Agents

Suitable physiological cooling agents may be selected from the groupconsisting of menthol, menthone glycerol acetal, menthone glycerylketal, menthyl lactate preferably l-menthyl lactate, in particularl-menthyl l-lactate), menthyl ethyl oxamate, substitutedmenthyl-3-carboxylic acid amides (e.g. menthyl-3-carboxylic acidN-ethylamide, N^(a)-(L-menthanecarbonyl)glycine ethyl ester,2-isopropyl-N-2,3-trimethylbutanamide, substituted cyclohexanecarboxylicacid amides, 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthylcarbonate, 2-hydroxypropyl menthyl carbonate, N-acetylglycine menthylester, isopulegol, menthyl hydroxycarboxylic acid esters (e.g. menthyl3-hydroxybutyrate), monomenthyl succinate, monomenthyl glutarate,2-mercaptocyclodecanone, menthyl 2-pyrrolidin-5-onecarboxylate,2,3-dihydroxy-p-menthane, 3,3,5-trimethylcyclohexanone glycerol ketal,3-menthyl 3,6-di- and -trioxaalkanoates, 3-menthyl methoxyacetate andicilin.

Anti-Microbial Agents

Suitable anti-microbial agents are, in principle, all substanceseffective against Gram-positive bacteria, such as, for example,4-hydroxybenzoic acid and its salts and esters,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea,2,4,4′-trichloro-2′-hydroxy-diphenyl ether (triclosan),4-chloro-3,5-dimethyl-phenol, 2,2′-methylenebis(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chloro-phenol,3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialfragrances, thymol, thyme oil, eugenol, oil of cloves, menthol, mintoil, farnesol, phenoxyethanol, glycerol monocaprate, glycerolmonocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC),salicylic acid N-alkylamides, such as, for example, n-octylsalicylamideor n-decylsalicylamide.

Enzyme Inhibitors

Suitable enzyme inhibitors are, for example, esterase inhibitors. Theseare preferably trialkyl citrates, such as trimethyl citrate, tripropylcitrate, triisopropyl citrate, tributyl citrate and, in particular,triethyl citrate (Hydagen CAT). The substances inhibit enzyme activity,thereby reducing the formation of odour. Other substances which aresuitable esterase inhibitors are sterol sulfates or phosphates, such as,for example, lanosterol, cholesterol, campesterol, stigmasterol andsitosterol sulfate or phosphate, dicarboxylic acids and esters thereof,such as, for example, glutaric acid, monoethyl glutarate, diethylglutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acidand diethyl malonate, hydroxycarboxylic acids and esters thereof, suchas, for example, citric acid, malic acid, tartaric acid or diethyltartrate, and zinc glycinate.

Odour Absorbers and Antiperspirant Active Agents

Suitable odour absorbers are substances which are able to absorb andlargely retain odour-forming compounds. They lower the partial pressureof the individual components, thus also reducing their rate ofdiffusion. It is important that perfumes must remain unimpaired in thisprocess. Odour absorbers are not effective against bacteria. Theycomprise, for example, as main constituent, a complex zinc salt ofricinoleic acid or specific, largely odour-neutral fragrances which areknown to the person skilled in the art as “fixatives”, such as, forexample, extracts of labdanum or styrax or certain abietic acidderivatives. The odour masking agents are fragrances or perfume oils,which, in addition to their function as odour masking agents, give thedeodorants their respective fragrance note. Perfume oils which may bementioned are, for example, mixtures of natural and syntheticfragrances. Natural fragrances are extracts from flowers, stems andleaves, fruits, fruit peels, roots, woods, herbs and grasses, needlesand branches, and resins and balsams. Also suitable are animal products,such as, for example, civet and castoreum. Typical synthetic fragrancecompounds are products of the ester, ether, aldehyde, ketone, alcohol,and hydrocarbon type. Fragrance compounds of the ester type are, forexample, benzyl acetate, p-tert-butylcyclohexyl acetate, linalylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. Theethers include, for example, benzyl ethyl ether, and the aldehydesinclude, for example, the linear alkanals having 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxycitronellal, lilial and bourgeonal, the ketones include, forexample, the ionones and methyl cedryl ketone, the alcohols includeanethole, citronellol, eugenol, isoeugenol, geraniol, linaool,phenylethyl alcohol and terpineol, and the hydrocarbons include mainlythe terpenes and balsams. Preference is, however, given to usingmixtures of different fragrances which together produce a pleasingfragrance note. Essential oils of relatively low volatility, which aremostly used as aroma components, are also suitable as perfume oils, e.g.sage oil, camomile oil, oil of cloves, melissa oil, mint oil, cinnamonleaf oil, linden flower oil, juniperberry oil, vetiver oil, olibanumoil, galbanum oil, labdanum oil and lavandin oil. Preference is given tousing bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone,cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole,hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone,geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur,iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid,geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl andfloramat alone or in mixtures.

Suitable astringent antiperspirant active ingredients are primarilysalts of aluminium, zirconium or of zinc. Such suitable antihydroticactive ingredients are, for example, aluminium chloride, aluminiumchlorohydrate, aluminium dichlorohydrate, aluminium sesquichlorohydrateand complex compounds thereof, e.g. with 1,2-propylene glycol, aluminiumhydroxyallantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof, e.g. withamino acids, such as glycine.

Film Formers and Anti-Dandruff Agents

Standard film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinyl pyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof and similar compounds.

Suitable antidandruff agents are Pirocton Olamin(1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinonemonoethanolamine salt), Baypival (Climbazole), Ketoconazol®(4-acetyl-1-{4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine,ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate,sulfur tar distillate, salicylic acid (or in combination withhexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein/undecylenic acid condensate), zincpyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Carriers and Hydrotropes

Preferred cosmetics carrier materials are solid or liquid at 25° C. and1013 mbar (including highly viscous substances) as for example glycerol,1,2-propylene glycol, 1,2-butylene glycol, 1,3-propylene glycol,1,3-butylene glycol, ethanol, water and mixtures of two or more of saidliquid carrier materials with water. Optionally, these preparationsaccording to the invention may be produced using preservatives orsolubilizers. Other preferred liquid carrier substances, which may be acomponent of a preparation according to the invention are selected fromthe group consisting of oils such as vegetable oil, neutral oil andmineral oil.

Preferred solid carrier materials, which may be a component of apreparation according to the invention are hydrocolloids, such asstarches, degraded starches, chemically or physically modified starches,dextrins, (powdery) maltodextrins (preferably with a dextrose equivalentvalue of 5 to 25, preferably of 10-20), lactose, silicon dioxide,glucose, modified celluloses, gum arabic, ghatti gum, traganth, karaya,carrageenan, pullulan, curdlan, xanthan gum, gellan gum, guar flour,carob bean flour, alginates, agar, pectin and inulin and mixtures of twoor more of these solids, in particular maltodextrins (preferably with adextrose equivalent value of 15-20), lactose, silicon dioxide and/orglucose.

In addition, hydrotropes, for example ethanol, isopropyl alcohol orpolyols, may be used to improve flow behaviour. Suitable polyolspreferably contain 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols may contain other functional groups, more especiallyamino groups, or may be modified with nitrogen. Typical examples are

-   -   glycerol;    -   alkylene glycols such as, for example, ethylene glycol,        diethylene glycol, propylene glycol, butylene glycol, hexylene        glycol and polyethylene glycols with an average molecular weight        of 100 to 1000 Dalton;    -   technical oligoglycerol mixtures with a degree of        self-condensation of 1.5 to 10, such as for example technical        diglycerol mixtures with a diglycerol content of 40 to 50% by        weight;    -   methylol compounds such as, in particular, trimethylol ethane,        trimethylol propane, trimethylol butane, pentaerythritol and        dipentaerythritol;    -   lower alkyl glucosides, particularly those containing 1 to 8        carbon atoms in the alkyl group, for example methyl and butyl        glucoside;    -   sugar alcohols containing 5 to 12 carbon atoms, for example        sorbitol or mannitol,    -   sugars containing 5 to 12 carbon atoms, for example glucose or        sucrose;    -   amino sugars, for example glucamine;    -   dialcoholamines, such as diethanolamine or        2-aminopropane-1,3-diol.

Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid and the other classes ofcompounds listed in Appendix 6, Parts A and B of the Kosmetikverordnung(“Cosmetics Directive”).

Perfume Oils and Fragrances

Suitable perfume oils are mixtures of natural and synthetic perfumes.Natural perfumes include the extracts of blossoms (lily, lavender, rose,jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli,petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel(bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom,costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood,cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage,thyme), needles and branches (spruce, fir, pine, dwarf pine), resins andbalsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animalraw materials, for example civet and beaver, may also be used. Typicalsynthetic perfume compounds are products of the ester, ether, aldehyde,ketone, alcohol and hydrocarbon type. Examples of perfume compounds ofthe ester type are benzyl acetate, phenoxyethyl isobutyrate,p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzylcarbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzylformate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate,styrallyl propionate and benzyl salicylate. Ethers include, for example,benzyl ethyl ether while aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal. Examples of suitable ketones are the ionones,

-isomethylionone and methyl cedryl ketone. Suitable alcohols areanethol, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol. The hydrocarbons mainly include theterpenes and balsams. However, it is preferred to use mixtures ofdifferent perfume compounds which, together, produce an agreeableperfume. Other suitable perfume oils are essential oils of relativelylow volatility which are mostly used as aroma components. Examples aresage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, ladanum oil and lavendin oil. The following are preferablyused either individually or in the form of mixtures: bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice,citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal,lavendin oil, clary oil, damascone, geranium oil bourbon, cyclohexylsalicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldeingamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,romillat, irotyl and floramat.

Dyes

Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Färbemittel” of the Farbstoff-kommission der DeutschenForschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.Examples include cochineal red A (C.I. 16255), patent blue V (C.I.42051), indigotin (C.I. 73015), chlorophyllin (C.I. 75810), quinolineyellow (C.I. 47005), titanium dioxide (C.I. 77891), indanthrene blue RS(C.I. 69800) and madder lake (C.I. 58000). Luminol may also be presentas a luminescent dye. Advantageous coloured pigments are for exampletitanium dioxide, mica, iron oxides (e.g. Fe₂O₃ Fe₃O₄, FeO (OH)) and/ortin oxide. Advantageous dyes are for example carmine, Berlin blue,chromium oxide green, ultramarine blue and/or manganese violet.

Preparations

Preferred compositions according to the present inventions are selectedfrom the group of products for treatment, protecting, care and cleansingof the skin and/or hair or as a make-up product, preferably as aleave-on product (meaning that the one or more compounds of formula (I)stay on the skin and/or hair for a longer period of time, compared torinse-off products, so that the moisturizing and/or anti-ageing and/orwound healing promoting action thereof is more pronounced).

The formulations according to the invention are preferably in the formof an emulsion, e.g. W/O (water-in-oil), O/W (oil-in-water), W/O/W(water-in-oil-in-water), O/W/O (oil-in-water-in-oil) emulsion, PITemulsion, Pickering emulsion, emulsion with a low oil content, micro- ornanoemulsion, a solution, e.g. in oil (fatty oils or fatty acid esters,in particular C₆-C₃₂ fatty acid C₂-C₃₀ esters) or silicone oil,dispersion, suspension, creme, lotion or milk, depending on theproduction method and ingredients, a gel (including hydrogel,hydrodispersion gel, oleogel), spray (e.g. pump spray or spray withpropellant) or a foam or an impregnating solution for cosmetic wipes, adetergent, e.g. soap, synthetic detergent, liquid washing, shower andbath preparation, bath product (capsule, oil, tablet, salt, bath salt,soap, etc.), effervescent preparation, a skin care product such as e.g.an emulsion (as described above), ointment, paste, gel (as describedabove), oil, balsam, serum, powder (e.g. face powder, body powder), amask, a pencil, stick, roll-on, pump, aerosol (foaming, non-foaming orpost-foaming), a deodorant and/or antiperspirant, mouthwash and mouthrinse, a foot care product (including keratolytic, deodorant), an insectrepellent, a sunscreen, aftersun preparation, a shaving product,aftershave balm, pre- and aftershave lotion, a depilatory agent, a haircare product such as e.g. shampoo (including 2-in-1 shampoo,anti-dandruff shampoo, baby shampoo, shampoo for dry scalps,concentrated shampoo), conditioner, hair tonic, hair water, hair rinse,styling creme, pomade, perm and setting lotion, hair spray, styling aid(e.g. gel or wax), hair smoothing agent (detangling agent, relaxer),hair dye such as e.g. temporary direct-dyeing hair dye, semi-permanenthair dye, permanent hair dye, hair conditioner, hair mousse, eye careproduct, make-up, make-up remover or baby product.

The formulations according to the invention are particularly preferablyin the form of an emulsion, in particular in the form of a W/O, O/W,W/O/W, O/W/O emulsion, PIT emulsion, Pickering emulsion, emulsion with alow oil content, micro- or nanoemulsion, a gel (including hydrogel,hydrodispersion gel, oleogel), a solution e.g. in oil (fatty oils orfatty acid esters, in particular C₆-C₃₂ fatty acid C₂-C₃₀ esters)) orsilicone oil, or a spray (e.g. pump spray or spray with propellant).

Auxiliary substances and additives can be included in quantities of 5 to99% b.w., preferably 10 to 80% b.w., based on the total weight of theformulation. The amounts of cosmetic or dermatological auxiliary agentsand additives and perfume to be used in each case can easily bedetermined by the person skilled in the art by simple trial and error,depending on the nature of the particular product.

The preparations can also contain water in a quantity of up to 99% b.w.,preferably 5 to 80% b.w., based on the total weight of the preparation.

Household Compositions

Another object of the present invention refers to household or detergentcompositions either comprising the mixture of components (a), (b), (c)and optionally (d) as described above or the perfume compositionscomprising them. Suitable examples for household and detergent productsencompass heavy duty powder detergents, heavy duty liquid detergents,light duty powder detergents, light duty liquid detergents, fabricsofteners, manual dish wash agents, all-purpose cleaners and the like.

The detergent compositions according to the present invention maycomprise any of the ingredients customarily found in such compositions,such as, for example, anionic, nonionic, cationic, amphoteric orzwitterionic (co-)surfactants, organic solvents, builders, enzymes andadditional auxiliaries such as soil repellents, thickeners, colorantsand fragrances or the like.

Anionic Co-Surfactants

Preferably, surfactants of the sulfonate type, alk(en)yl sulfonates,alkoxylated alk(en)yl sulfates, ester sulfonates and/or soaps are usedas the anionic surfactants. Suitable surfactants of the sulfonate typeare advantageously C₉₋₁₃ alkylbenzene sulfonates, olefin sulfonates,i.e. mixtures of alkene- and hydroxyalkane sulfonates, and disulfonates,as are obtained, for example, by the sulfonation with gaseous sulfurtrioxide of C₁₂₋₁₈ monoolefins having a terminal or internal double bondand subsequent alkaline or acidic hydrolysis of the sulfonationproducts.

Alk(en)yl sulfates. Preferred alk(en)yl sulfates are the alkali andespecially the sodium salts of the sulfuric acid half-esters of theC₁₂-C₁₈ fatty alcohols, for example, from coconut butter alcohol, tallowalcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C₈-C₂₀ oxoalcohols and those half-esters of secondary alcohols of these chainlengths. Alk(en)yl sulfates of the cited chain lengths that comprise asynthetic straight chain alkyl group manufactured petrochemically arealso preferred. The C₁₂-C₁₆ alkyl sulfates and C₁₂-C₁₅ alkyl sulfates aswell as C₁₄-C₁₅ alkyl sulfates and C₁₄-C₁₆ alkyl sulfates areparticularly preferred on the grounds of laundry performance. The2,3-alkyl sulfates, which can be obtained from Shell Oil Company underthe trade name DAN™, are also suitable anionic surfactants.

Alk(en)yl ether sulfates. Sulfuric acid mono-esters derived fromstraight-chained or branched C₇-C₂₁ alcohols ethoxylated with 1 to 6moles ethylene oxide are also suitable, such as 2-methyl-branched C₉-C₁₁alcohols with an average of 3.5 mol ethylene oxide (EO) or C₁₂-C₁₈ fattyalcohols with 1 to 4 EO.

Ester sulfonates. The esters of alpha-sulfo fatty acids (estersulfonates), e.g., the alpha-sulfonated methyl esters of hydrogenatedcoco-, palm nut- or tallow acids are likewise suitable.

Soaps. Soaps, in particular, can be considered as further anionicsurfactants. Saturated fatty acid soaps are particularly suitable, suchas the salts of lauric acid, myristic acid, palmitic acid, stearic acid,hydrogenated erucic acid and behenic acid, and especially soap mixturesderived from natural fatty acids such as coconut oil fatty acid, palmkernel oil fatty acid or tallow fatty acid. Those soap mixtures areparticularly preferred that are composed of 50 to 100 wt. % of saturatedC₁₂-C₂₄ fatty acid soaps and 0 to 50 wt. % of oleic acid soap.

Ether carboxylic acids. A further class of anionic surfactants is thatof the ether carboxylic acids, obtainable by treating fatty alcoholethoxylates with sodium chloroacetate in the presence of basiccatalysts. They have the general formula: RO(CH₂CH₂O)_(p)CH₂COOH withR═C₁-C₁₈ and p=0.1 to 20. Ether carboxylic acids are insensitive towater hardness and possess excellent surfactant properties.

Non-Ionic (Co-)Surfactants

Alkohol alkoxylates. The added nonionic surfactants are preferablyalkoxylated and/or propoxylated, particularly primary alcohols havingpreferably 8 to 18 carbon atoms and an average of 1 to 12 mol ethyleneoxide (EO) and/or 1 to 10 mol propylene oxide (PO) per mol alcohol.C₈-C₁₆-Alcohol alkoxylates, advantageously ethoxylated and/orpropoxylated C₁₀-C₁₅-alcohol alkoxylates, particularly C₁₂-C₁₄ alcoholalkoxylates, with an ethoxylation degree between 2 and 10, preferablybetween 3 and 8, and/or a propoxylation degree between 1 and 6,preferably between 1.5 and 5, are particularly preferred. The citeddegrees of ethoxylation and propoxylation constitute statistical averagevalues that can be a whole or a fractional number for a specificproduct. Preferred alcohol ethoxylates and propoxylates have a narrowedhomolog distribution (narrow range ethoxylates/propoxylates, NRE/NRP).In addition to these nonionic surfactants, fatty alcohols with more than12 EO can also be used. Examples of these are (tallow) fatty alcoholswith 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Alkylglycosides (APO. Furthermore, as additional nonionic surfactants,alkyl glycosides that satisfy the general Formula RO(G)_(x), can beadded, e.g., as compounds, particularly with anionic surfactants, inwhich R means a primary linear or methyl-branched, particularly2-methyl-branched, aliphatic group containing 8 to 22, preferably 12 to18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbonatoms, preferably for glucose. The degree of oligomerization x, whichdefines the distribution of monoglycosides and oligoglycosides, is anynumber between 1 and 10, preferably between 1.1 and 1.4.

Fatty acid ester alkoxylates. Another class of preferred nonionicsurfactants, which are used either as the sole nonionic surfactant or incombination with other nonionic surfactants, in particular, togetherwith alkoxylated fatty alcohols and/or alkyl glycosides, arealkoxylated, preferably ethoxylated or ethoxylated and propoxylatedfatty acid alkyl esters preferably containing 1 to 4 carbon atoms in thealkyl chain, more particularly the fatty acid methyl esters which aredescribed, for example, in Japanese Patent Application JP-A-58/217598 orwhich are preferably produced by the process described in InternationalPatent Application WO-A-90/13533. Methyl esters of C₁₂-C₁₈ fatty acidscontaining an average of 3 to 15 EO, particularly containing an averageof 5 to 12 EO, are particularly preferred.

Amine oxides. Nonionic surfactants of the amine oxide type, for example,N-coco alkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamidesmay also be suitable. The quantity in which these nonionic surfactantsare used is preferably no more than the quantity in which theethoxylated fatty alcohols are used and, particularly no more than halfthat quantity.

Gemini surfactants. The so-called gemini surfactants can be consideredas further surfactants. Generally speaking, such compounds areunderstood to mean compounds that have two hydrophilic groups and twohydrophobic groups per molecule. As a rule, these groups are separatedfrom one another by a “spacer”. The spacer is usually a hydrocarbonchain that is intended to be long enough such that the hydrophilicgroups are a sufficient distance apart to be able to act independentlyof one another. These types of surfactants are generally characterizedby an unusually low critical micelle concentration and the ability tostrongly reduce the surface tension of water. In exceptional cases,however, not only dimeric but also trimeric surfactants are meant by theterm gemini surfactants. Suitable gemini surfactants are, for example,sulfated hydroxy mixed ethers according to German Patent Application DE4321022 A1 or dimer alcohol bis- and trimer alcohol tris sulfates andether sulfates according to International Patent Application WO 96/23768A1. Blocked end group dimeric and trimeric mixed ethers according toGerman Patent Application DE 19513391 A1 are especially characterized bytheir bifunctionality and multifunctionality. Gemini polyhydroxyfattyacid amides or polyhydroxyfatty acid amides, such as those described inInternational Patent Applications WO 95/19953 A1, WO 95/19954 A1 and WO95/19955 A1 can also be used.

Cationic Co-Surfactants

Tetraalkyl ammonium salts. Cationically active surfactants comprise thehydrophobic high molecular group required for the surface activity inthe cation by dissociation in aqueous solution. A group of importantrepresentatives of the cationic surfactants are the tetraalkyl ammoniumsalts of the general formula: (R¹R²R³R⁴N⁺) X⁻. Here R1 stands for C₁-C₈alk(en)yl, R², R³ and R⁴, independently of each other, for alk(en)ylradicals having 1 to 22 carbon atoms. X is a counter ion, preferablyselected from the group of the halides, alkyl sulfates and alkylcarbonates. Cationic surfactants, in which the nitrogen group issubstituted with two long acyl groups and two short alk(en)yl groups,are particularly preferred.

Esterquats. A further class of cationic surfactants particularly usefulas co-surfactants for the present invention is represented by theso-called esterquats. Esterquats are generally understood to bequaternised fatty acid triethanolamine ester salts. These are knowncompounds which can be obtained by the relevant methods of preparativeorganic chemistry. Reference is made in this connection to Internationalpatent application WO 91/01295 A1, according to which triethanolamine ispartly esterified with fatty acids in the presence of hypophosphorousacid, air is passed through the reaction mixture and the whole is thenquaternised with dimethyl sulphate or ethylene oxide. In addition,German patent DE 4308794 C1 describes a process for the production ofsolid esterquats in which the quaternisation of triethanolamine estersis carried out in the presence of suitable dispersants, preferably fattyalcohols.

Typical examples of esterquats suitable for use in accordance with theinvention are products of which the acyl component derives frommonocarboxylic acids corresponding to formula RCOOH in which RCO is anacyl group containing 6 to 10 carbon atoms, and the amine component istriethanolamine (TEA). Examples of such monocarboxylic acids are caproicacid, caprylic acid, capric acid and technical mixtures thereof such as,for example, so-called head-fractionated fatty acid. Esterquats of whichthe acyl component derives from monocarboxylic acids containing 8 to 10carbon atoms, are preferably used. Other esterquats are those of whichthe acyl component derives from dicarboxylic acids like malonic acid,succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid,pimelic acid, azelaic acid, sebacic acid and/or dodecanedioic acid, butpreferably adipic acid. Overall, esterquats of which the acyl componentderives from mixtures of monocarboxylic acids containing 6 to 22 carbonatoms, and adipic acid are preferably used. The molar ratio of mono anddicarboxylic acids in the final esterquat may be in the range from 1:99to 99:1 and is preferably in the range from 50:50 to 90:10 and moreparticularly in the range from 70:30 to 80:20. Besides the quaternisedfatty acid triethanolamine ester salts, other suitable esterquats arequaternized ester salts of mono-/dicarboxylic acid mixtures withdiethanolalkyamines or 1,2-dihydroxypropyl dialkylamines. The esterquatsmay be obtained both from fatty acids and from the correspondingtriglycerides in admixture with the corresponding dicarboxylic acids.One such process, which is intended to be representative of the relevantprior art, is proposed in European patent EP 0750606 B1. To produce thequaternised esters, the mixtures of mono- and dicarboxylic acids and thetriethanolamine—based on the available carboxyl functions—may be used ina molar ratio of 1.1:1 to 3:1. With the performance properties of theesterquats in mind, a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to1.9:1 has proved to be particularly advantageous. The preferredesterquats are technical mixtures of mono-, di- and triesters with anaverage degree of esterification of 1.5 to 1.9.

Amphoteric or Zwitterionic Co-Surfactants

Betaines. Amphoteric or ampholytic surfactants possess a plurality offunctional groups that can ionize in aqueous solution andthereby—depending on the conditions of the medium—lend anionic orcationic character to the compounds (see DIN 53900, July 1972). Close tothe isoelectric point (around pH 4), the amphoteric surfactants forminner salts, thus becoming poorly soluble or insoluble in water.Amphoteric surfactants are subdivided into ampholytes and betaines, thelatter existing as zwitterions in solution. Ampholytes are amphotericelectrolytes, i.e. compounds that possess both acidic as well as basichydrophilic groups and therefore behave as acids or as bases dependingon the conditions. Especially betaines are known surfactants which aremainly produced by carboxyalkylation, preferably carboxymethylation, ofamine compounds. The starting materials are preferably condensed withhalocarboxylic acids or salts thereof, more particularly sodiumchloroacetate, one mole of salt being formed per mole of betaine. Theaddition of unsaturated carboxylic acids, such as acrylic acid forexample, is also possible. Examples of suitable betaines are the carboxyalkylation products of secondary and, in particular, tertiary amineswhich correspond to formula R¹R²R³N—(CH₂)_(q)COOX where R¹ is a an alkylradical having 6 to 22 carbon atoms, R² is hydrogen or an alkyl groupcontaining 1 to 4 carbon atoms, R³ is an alkyl group containing 1 to 4carbon atoms, q is a number of 1 to 6 and X is an alkali and/or alkalineearth metal or ammonium. Typical examples are the carboxymethylationproducts of hexylmethylamine, hexyldimethylamine, octyldimethylamine,decyldimethylamine, C_(12/14)-cocoalkyldimethyl-amine,myristyldimethylamine, cetyldimethylamine, stearyldimethylamine,stearylethylmethylamine, oleyldimethylamine,C_(16/18)-tallowalkyldimethylamine and their technical mixtures, andparticularly dodecyl methylamine, dodecyl dimethylamine, dodecylethylmethylamine and technical mixtures thereof.

Alkylamido betaines. Other suitable betaines are the carboxyalkylationproducts of amidoamines corresponding to formulaR¹CO(R³)(R⁴)—NH—(CH₂)_(p)—N—(CH₂)_(q)COOX in which R¹CO is an aliphaticacyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds,R² is hydrogen or an alkyl radical having 1 to 4 carbon atoms, R³ is analkyl radical having 1 to 4 carbon atoms, p is a number from 1 to 6, qis a number from 1 to 3 and X is an alkali and/or alkaline earth metalor ammonium. Typical examples are reaction products of fatty acidshaving 6 to 22 carbon atoms, like for example caproic acid, caprylicacid, caprinic acid, lauric acid, myristic acid, palmitic acid,palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselinic acid, linolic acid linoleic acid, elaeostearic acid,arachidonic acid, gadoleic acid, behenic acid, erucic acid and theirtechnical mixtures with N,N-dimethylaminoethylamine,N,N-dimethylaminopropylamine, N,N-diethylaminoethylamine andN,N-diethylaminopropylamine, which are condensed with sodiumchloroacetate. The commercially available products include Dehyton® Kand Dehyton® PK (Cognis Deutschland GmbH & Co., KG) as well asTego®Betaine (Goldschmidt).

Imidazolines. Other suitable starting materials for the betaines to beused for the purposes of the invention are imidazolines. Thesesubstances are also known and may be obtained, for example, by cyclizingcondensation of 1 or 2 moles of C₆ ⁻C₂₂ fatty acids with polyfunctionalamines, such as for example aminoethyl ethanolamine (AEEA) ordiethylenetriamine. The corresponding carboxyalkylation products aremixtures of different open-chain betaines. Typical examples arecondensation products of the above-mentioned fatty acids with AEEA,preferably imidazolines based on lauric acid, which are subsequentlybetainised with sodium chloroacetate. The commercially availableproducts include Dehyton® G (Cognis Deutschland GmbH & Co., KG)

The amount of (co-)surfactant comprised in the inventive compositions isadvantageously 0.1 wt. % to 90 wt. %, particularly 10 wt. % to 80 wt. %and particularly preferably 20 wt. % to 70 wt.-%.

Organic Solvents

Liquid light or heavy duty detergents may comprise organic solvents,preferably those miscible with water. Polydiols, ethers, alcohols,ketones, amides and/or esters are preferably used as the organic solventfor this in amounts of 0 to 90 wt. %, preferably 0.1 to 70 wt. %,particularly 0.1 to 60 wt. %. Low molecular weight polar substances,such as for example, methanol, ethanol, propylene carbonate, acetone,acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethyleneglycol, propylene glycol, glycerin, diethylene glycol, dipropyleneglycol monomethyl ether and dimethylformamide or their mixtures arepreferred.

Enzymes

Cellulase Enzymes. Cellulase enzymes optionally used in the instantdetergent composition are preferably incorporated, when present, atlevels sufficient to provide up to about 5 mg by weight, more preferablyabout 0.01 mg to about 3 mg, of active enzyme per gram of thecomposition. Unless stated otherwise, the compositions herein preferablycomprise from about 0.001% to about 5%, preferably 0.01%-1% by weight ofa commercial enzyme preparation.

The cellulases suitable for the present invention include eitherbacterial or fungal cellulase. Preferably, they will have a pH optimumof between 5 and 9.5. Suitable cellulases are fungal cellulase producedfrom Humicola insolens and Humicola strain DSM1800 or a cellulase212-producing fungus belonging to the genus Aeromonas, and cellulaseextracted from the hepatopancreas of a marine mollusk (DolabellaAuricula Solander), suitable cellulases are also disclosed in GB2,075,028 A. In addition, cellulase especially suitable for use hereinare disclosed in WO 1992 013057 A1. Most preferably, the cellulases usedin the instant detergent compositions are purchased commercially fromNOVO Industries A/S under the product names CAREZYMEO and CELLUZYMEO.

Other Enzymes. Additional enzymes can be included in the detergentcompositions herein for a wide variety of fabric laundering purposes,including removal of protein-based, carbohydrate-based, ortriglyceride-based stains, for example, and for the prevention ofrefugee dye transfer, and for fabric restoration. The additional enzymesto be incorporated include proteases, amylases, lipases, andperoxidases, as well as mixtures thereof. Other types of enzymes canalso be included. They can be of any suitable origin, such as vegetable,animal, bacterial, fungal and yeast origin. However, their choice isgoverned by several factors such as pH-activity and/or stability optima,thermostability, stability versus active detergents, builders as well astheir potential to cause malodors during use. In this respect bacterialor fungal enzymes are preferred, such as bacterial amylases andproteases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.01 mg to about 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from about 0.001% to about5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE®. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 of Novo. Proteolytic enzymes suitable for removingprotein-based stains that are commercially available include those soldunder the trade names ALCALASE® and SAVINASE® by Novo Industries A/S andMAXATASE® by International Bio-Synthetics, Inc. Other proteases includeProtease A; Protease B and proteases made by Genencor International,Inc., according to U.S. Pat. No. 5,204,015 and U.S. Pat. No. 5,244,791.

Amylases include, for example, alpha-amylases like RAPIDASE®,International Bio-Synthetics, Inc. and TERMAMYL®, Novo Industries.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19154. This lipase is available from Amano Pharmaceutical Co. Ltd.,under the trade name Lipase P “Amano”. Other commercial lipases includeAmano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosumvar. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,and further Chromobacter viscosum lipases from U.S. Biochemical Corp.and Disoynth Co., and lipases ex Pseudomonas gladioli. The LIPOLASE®enzyme derived from Humicola lanuginosa (commercially available fromNovo Industries A/S) is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for “solution bleaching,” i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in WO 1989 099813 A1.

Enzyme Stabilizers. The enzymes employed herein are stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished detergent compositions which provide such ions to theenzymes. (Calcium ions are generally somewhat more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used.) Additional stability can be provided by the presence ofvarious other art-disclosed stabilizers, especially borate species, seeU.S. Pat. No. 4,537,706, incorporated herein in its entirety. Typicaldetergents, especially liquids, will comprise from about 1 to about 30,preferably from about 2 to about 20, more preferably from about 5 toabout 15, and most preferably from about 8 to about 12, millimoles ofcalcium ion per liter of finished composition. In solid detergentcompositions the formulation can include a sufficient quantity of awater-soluble calcium ion source to provide such amounts in the laundryliquor. In the alternative, natural water hardness can suffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance. Accordingly, as ageneral proposition the compositions herein will typically comprise fromabout 0.05% to about 2% by weight of a water-soluble source of calciumor magnesium ions, or both. The amount can vary, of course, with theamount and type of enzyme employed in the composition.

The compositions herein can also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom about 0.25% to about 10%, preferably from about 0.5% to about 5%,more preferably from about 0.75% to about 3%, by weight of boric acid orother borate compound capable of forming boric acid in the composition(calculated on the basis of boric acid). Boric acid is preferred,although other compounds such as boric oxide, borax and other alkalimetal borates (e.g., sodium ortho-, meta- and pyroborate, and sodiumpentaborate) are suitable. Substituted boric acids (e.g., phenylboronicacid, butane boronic acid, and p-bromo phenylboronic acid) can also beused in place of boric acid.

Builders

Zeolites. Fine crystalline, synthetic zeolites containing bound watercan be used as builders, for example, preferably zeolite A and/or P.Zeolite MAP® (commercial product of the Crosfield company), isparticularly preferred as the zeolite P. However, zeolite X and mixturesof A, X, Y and/or P are also suitable. A co-crystallizedsodium/potassium aluminum silicate from Zeolite A and Zeolite X, whichis available as Vegobond RX. (commercial product from Condea AugustaS.p.A.), is also of particular interest. Preferably, the zeolite can beused as a spray-dried powder. For the case where the zeolite is added asa suspension, this can comprise small amounts of nonionic surfactants asstabilizers, for example, 1 to 3 wt. %, based on the zeolite, ofethoxylated C₁₂-C₁₈ fatty alcohols with 2 to 5 ethylene oxide groups,C₁₂-C₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylatedisotridecanols. Suitable zeolites have an average particle size of lessthan 10 μm (test method: volumetric distribution Coulter counter) andpreferably comprise 18 to 22 wt. %, particularly 20 to 22 wt. % of boundwater. Apart from this, phosphates can also be used as builders.

Layered silicates. Suitable substitutes or partial substitutes forphosphates and zeolites are crystalline, layered sodium silicates. Thesetypes of crystalline layered silicates are described, for example, inEuropean Patent Application EP 0164514 A1. Preferred crystalline layeredsilicates are those obtained for example, from the process described inInternational Patent Application WO 91/08171 A1.

Amorphous silicates. Preferred builders also include amorphous sodiumsilicates with a modulus (Na₂O:SiO₂ ratio) of 1:2 to 1:3.3, preferably1:2 to 1:2.8 and more preferably 1:2 to 1:2.6, which dissolve with adelay and exhibit multiple wash cycle properties. The delay indissolution compared with conventional amorphous sodium silicates canhave been obtained in various ways, for example, by surface treatment,compounding, compressing/compacting or by over-drying. In the context ofthis invention, the term “amorphous” also means “X-ray amorphous”. Inother words, the silicates do not produce any of the sharp X-rayreflexions typical of crystalline substances in X-ray diffractionexperiments, but at best one or more maxima of the scatteredX-radiation, which have a width of several degrees of the diffractionangle. However, particularly good builder properties may even beachieved where the silicate particles produce indistinct or even sharpdiffraction maxima in electron diffraction experiments. This is to beinterpreted to mean that the products have microcrystalline regionsbetween 10 and a few hundred nm in size, values of up to at most 50 nmand especially up to at most 20 nm being preferred. This type of X-rayamorphous silicates, which similarly possess a delayed dissolution incomparison with the customary water glasses, are described, for example,in German Patent Application DE 4400024 A1. Compacted/densifiedamorphous silicates, compounded amorphous silicates and over driedX-ray-amorphous silicates are particularly preferred.

Phosphates. Also the generally known phosphates can also be added asbuilders, in so far that their use should not be avoided on ecologicalgrounds. The sodium salts of the orthophosphates, the pyrophosphates andespecially the tripolyphosphates are particularly suitable. Theircontent is generally not more than 25 wt. %, preferably not more than 20wt. %, each based on the finished composition. In some cases it has beenshown that particularly tripolyphosphates, already in low amounts up tomaximum 10 wt. %, based on the finished composition, in combination withother builders, lead to a synergistic improvement of the secondarywashing power. Preferred amounts of phosphates are under 10 wt. %,particularly 0 wt. %.

Co-Builders

Polycarboxylic acids. Useful organic cobuilders are, for example, thepolycarboxylic acids usable in the form of their sodium salts ofpolycarboxylic acids, wherein polycarboxylic acids are understood to becarboxylic acids that carry more than one acid function. These include,for example, citric acid, adipic acid, succinic acid, glutaric acid,malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids,aminocarboxylic acids, nitrilotriacetic acid (NTA) and its derivativesand mixtures thereof. Preferred salts are the salts of polycarboxylicacids such as citric acid, adipic acid, succinic acid, glutaric acid,tartaric acid, sugar acids and mixtures thereof.

Organic acids. Acids per se can also be used. Besides their buildingeffect, the acids also typically have the property of an acidifyingcomponent and, hence also serve to establish a relatively low and mildpH in detergents or cleansing compositions. Citric acid, succinic acid,glutaric acid, adipic acid, gluconic acid and any mixtures thereof areparticularly mentioned in this regard. Further suitable acidifiers arethe known pH regulators such as sodium hydrogen carbonate and sodiumhydrogen sulfate.

Polymers. Particularly suitable polymeric cobuilders are polyacrylates,which preferably have a molecular weight of 2,000 to 20,000 g/mol. Byvirtue of their superior solubility, preferred representatives of thisgroup are again the short-chain polyacrylates, which have molecularweights of 2,000 to 10,000 g/mol and, more particularly, 3,000 to 5,000g/mol. Suitable polymers can also include substances that consistpartially or totally of vinyl alcohol units or its derivatives.

Further suitable copolymeric polycarboxylates are particularly those ofacrylic acid with methacrylic acid and of acrylic acid or methacrylicacid with maleic acid. Copolymers of acrylic acid with maleic acid,which comprise 50 to 90 wt. % acrylic acid and 50 to 10 wt. % maleicacid, have proven to be particularly suitable. Their relative molecularweight, based on free acids, generally ranges from 2,000 to 70,000g/mol, preferably 20,000 to 50,000 g/mol and especially 30,000 to 40,000g/mol. The (co)polymeric polycarboxylates can be added either as anaqueous solution or preferably as powder. In order to improve the watersolubility, the polymers can also comprise allylsulfonic acids asmonomers, such as, for example, allyloxybenzene sulfonic acid andmethallyl sulfonic acid as in the EP 0727448 B1.

Biodegradable polymers comprising more than two different monomer unitsare particularly preferred, examples being those comprising, asmonomers, salts of acrylic acid and of maleic acid, and also vinylalcohol or vinyl alcohol derivatives, as in DE 4300772 A1, or thosecomprising, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and also sugar derivatives. Further preferred copolymersare those that are described in German Patent Applications DE 4303320 A1and DE 4417734 A1 and preferably include acrolein and acrylicacid/acrylic acid salts or acrolein and vinyl acetate as monomers.

Similarly, other preferred builders are polymeric aminodicarboxylicacids, salts or precursors thereof. Those polyaspartic acids or theirsalts and derivatives disclosed in German Patent Application DE 19540086A1 as having a bleach-stabilizing action in addition to cobuilderproperties are particularly preferred.

Further suitable builders are polyacetals that can be obtained bytreating dialdehydes with polyol carboxylic acids that possess 5 to 7carbon atoms and at least 3 hydroxyl groups, as described in EuropeanPatent Application EP 0280223 A1. Preferred polyacetals are obtainedfrom dialdehydes like glyoxal, glutaraldehyde, terephthalaldehyde aswell as their mixtures and from polycarboxylic acids like gluconic acidand/or glucoheptonic acid.

Carbohydrates. Further suitable organic cobuilders are dextrins, forexample, oligomers or polymers of carbohydrates that can be obtained bythe partial hydrolysis of starches. The hydrolysis can be carried outusing typical processes, for example, acidic or enzymatic catalyzedprocesses. The hydrolysis products preferably have average molecularweights in the range of 400 to 500,000 g/mol. A polysaccharide with adextrose equivalent (DE) of 0.5 to 40 and, more particularly, 2 to 30 ispreferred, the DE being an accepted measure of the reducing effect of apolysaccharide in comparison with dextrose, which has a DE of 100. Bothmaltodextrins with a DE between 3 and 20 and dry glucose syrups with aDE between 20 and 37 and also so-called yellow dextrins and whitedextrins with relatively high molecular weights of 2,000 to 30,000 g/molmay be used. A preferred dextrin is described in British PatentApplication 94 19 091.

The oxidized derivatives of such dextrins concern their reactionproducts with oxidizing compositions that are capable of oxidizing atleast one alcohol function of the saccharide ring to the carboxylic acidfunction. Such oxidized dextrins and processes for their manufacture areknown for example, from European Patent Applications EP 0232202 A1. Aproduct oxidized at C6 of the saccharide ring can be particularlyadvantageous.

Oxydisuccinates and other derivatives of disuccinates, preferablyethylenediamine disuccinate are also further suitable cobuilders. Here,ethylene diamine-N,N′-disuccinate (EDDS), the synthesis of which isdescribed for example, in U.S. Pat. No. 3,158,615, is preferably used inthe form of its sodium or magnesium salts. In this context, glycerinedisuccinates and glycerine trisuccinates are also particularlypreferred, such as those described in U.S. Pat. No. 4,524,009. Suitableaddition quantities in zeolite-containing and/or silicate-containingformulations range from 3 to 15% by weight.

(Lactones. Other useful organic co-builders are, for example, acetylatedhydroxycarboxylic acids and salts thereof which optionally may also bepresent in lactone form and which contain at least 4 carbon atoms, atleast one hydroxyl group and at most two acid groups. Such cobuildersare described, for example, in International Patent Application WO 1995020029 A1.

Bleaching Compounds, Bleaching Agents and Bleach Activators

The detergent compositions herein can optionally contain bleachingagents or bleaching compositions containing a bleaching agent and one ormore bleach activators. When present, bleaching agents will typically beat levels of from about 1% to about 30%, more typically from about 5% toabout 20%, of the detergent composition, especially for fabriclaundering. If present, the amount of bleach activators will typicallybe from about 0.1% to about 60%, more typically from about 0.5% to about40% of the bleaching composition comprising the bleachingagent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent “percarbonate” bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g.,OXONEO®, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.

Preferred amido-derived bleach activators include(6-octanamido-caproyl)oxybenzene-sulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxyben-zenesulfonate, and mixtures thereof.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed in U.S. Pat. No. 4,966,723, incorporated herein byreference.

Highly preferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof, optionally adsorbed into solid carriers, e.g acyl caprolactams,preferably benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such manganese-based catalysts are well known in theart and include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III)Mn^(IV) ₄ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), and mixturesthereof.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Polymeric Soil Release Agents

Any polymeric soil release agent known to those skilled in the art canoptionally be employed in the detergent compositions and processes ofthis invention. Polymeric soil release agents are characterized byhaving both hydrophilic segments, to hydrophilize the surface ofhydrophobic fibers, such as polyester and nylon, and hydrophobicsegments, to deposit upon hydrophobic fibers and remain adhered theretothrough completion of washing and rinsing cycles and, thus, serve as ananchor for the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to about 30 oxypropylene units wherein said mixture containsa sufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least about 25% oxyethylene units and more preferably,especially for such components having about 20 to 30 oxypropylene units,at least about 50% oxyethylene units; or (b) one or more hydrophobecomponents comprising (i) C₃ oxyalkylene terephthalate segments,wherein, if said hydrophobe components also comprise oxyethyleneterephthalate, the ratio of oxyethylene terephthalate: C₃ oxyalkyleneterephthalate units is about 2:1 or lower, (ii) C₄-C₆ alkylene or oxyC₄-C₆ alkylene segments, or mixtures therein, (iii) poly (vinyl ester)segments, preferably polyvinyl acetate), having a degree ofpolymerization of at least 2, or (iv) C₁-C₄ alkyl ether or C₄hydroxyalkyl ether substituents, or mixtures therein, wherein saidsubstituents are present in the form of C₁-C₄ alkyl ether or C₄hydroxyalkyl ether cellulose derivatives, or mixtures therein, and suchcellulose derivatives are amphiphilic, whereby they have a sufficientlevel of C₁-C₄ alkyl ether and/or C₄ hydroxyalkyl ether units to depositupon conventional polyester synthetic fiber surfaces and retain asufficient level of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilicity, or acombination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) will have a degree ofpolymerization of from about 200, although higher levels can be used,preferably from 3 to about 150, more preferably from 6 to about 100.Suitable oxy C₄-C₆ alkylene hydrophobe segments include, but are notlimited to, end-caps of polymeric soil release agents.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL® (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting ofC₁-C₄ alkyl and C₄ hydroxyalkyl cellulose.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁-C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones, see EP 0 219 048,incorporated herein in its entirety. Commercially available soil releaseagents of this kind include the SOKALAN® type of material, e.g.,SOKALAN® HP-22, available from BASF.

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentpreferably is in the range of from about 25,000 to about 55,000.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON® 5126 (from DuPont)and MILEASE® T (from ICI).

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451. Othersuitable polymeric soil release agents include the terephthalatepolyesters of U.S. Pat. No. 4,711,730, the anionic end-capped oligomericesters of U.S. Pat. No. 4,721,580, the block polyester oligomericcompounds of U.S. Pat. No. 4,702,857, and anionic, especiallysulfoaroyl, end-capped terephthalate esters of U.S. Pat. No. 4,877,896all cited patents incorporated herein in their entirety.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises about one sulfoisophthaloyl unit, 5 terephthaloylunits, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of fromabout 1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent alsocomprises from about 0.5% to about 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levelsfrom about 0.1% to about 7%, by weight, in the detergent compositionsherein, especially in the presence of zeolite and/or layered silicatebuilders. Suitable polymeric dispersing agents include polymericpolycarboxylates and polyethylene glycols, although others known in theart can also be used. It is believed, though it is not intended to belimited by theory, that polymeric dispersing agents enhance overalldetergent builder performance, when used in combination with otherbuilders (including lower molecular weight polycarboxylates) by crystalgrowth inhibition, particulate soil release peptization, andanti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example U.S. Pat. No. 3,308,067.

Acrylic/maleic-based copolymers can also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in EP 0193360 A1, which alsodescribes such polymers comprising hydroxypropylacrylate. Still otheruseful dispersing agents include the maleic/acrylic/vinyl alcoholterpolymers, for example, a 45/45/10 terpolymer of acrylic/maleic/vinylalcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents can also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Foam Inhibitors/Sud Supressors

Especially when used in automatic washing processes, it can beadvantageous to add conventional foam inhibitors to the compositions.Suitable foam inhibitors include for example, soaps of natural orsynthetic origin, which have a high content of C₁₈-C₂₄ fatty acids.Suitable non-surface-active types of foam inhibitors are, for example,organopolysiloxanes and mixtures thereof with microfine, optionallysilanised silica and also paraffins, waxes, microcrystalline waxes andmixtures thereof with silanised silica or bis-stearyl ethylenediamide.Mixtures of various foam inhibitors, for example, mixtures of silicones,paraffins or waxes, are also used with advantage. Preferably, the foaminhibitors, especially silicone-containing and/or paraffin-containingfoam inhibitors, are loaded onto a granular, water-soluble ordispersible carrier material. Especially in this case, mixtures ofparaffins and bis-stearylethylene diamides are preferred.

Compounds for reducing or suppressing the formation of suds can beincorporated into the detergent compositions of the present invention.Suds suppression can be of particular importance in the so-called “highconcentration cleaning process” and in front-loading European-stylewashing machines.

A wide variety of materials can be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein can also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphaticC₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout −40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.Hydrocarbon suds suppressors are known in the art and include aliphatic,alicyclic, aromatic, and heterocyclic saturated or unsaturatedhydrocarbons having from about 12 to about 70 carbon atoms. The term“paraffin,” as used in this suds suppressor discussion, is intended toinclude mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art.

Other silicone suds suppressors are disclosed in U.S. Pat. No.3,455,839, incorporated herein in its entirety, which relates tocompositions and processes for defoaming aqueous solutions byincorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance,in DE-OS 2124526, incorporated herein in its entirety. Siliconedefoamers and suds controlling agents in granular detergent compositionsare disclosed in U.S. Pat. No. 4,652,392, incorporated herein in itsentirety.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC® L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils. The secondary alcohols include the C₆-C₁₆ alkyl alcohols having aC₁-C₁₆ chain. A preferred alcohol is 2-butyl octanol, which is availablefrom Condea under the trademark ISOFOL® 12. Mixtures of secondaryalcohols are available under the trademark ISALCHEM® 123 from Enichem.Mixed suds suppressors typically comprise mixtures of alcohol+siliconeat a weight ratio of 1:5 to 5:1.

The compositions herein will generally comprise from 0% to about 5% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts can be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that can be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that can beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Sequestrants and Chelating Agents

The salts of polyphosphonic acid can be considered as sequestrants or asstabilizers, particularly for peroxy compounds and enzymes, which aresensitive towards heavy metal ions. Here, the sodium salts of, forexample, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylene phosphonate or ethylenediamine tetramethylene phosphonateare used in amounts of 0.1 to 5 wt. %.

The detergent compositions herein can also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Without intending to bebound by theory, it is believed that the benefit of these materials isdue in part to their exceptional ability to remove iron and manganeseions from washing solutions by formation of soluble chelates. It isunderstood that some of the detergent builders described hereinbeforecan function as chelating agents and is such detergent builder ispresent in a sufficient quantity, it can provide both functions.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetra proprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-Redeposition Agents

The detergent compositions of the present invention can also optionallycontain water-soluble ethoxylated amines having clay soil removal andantiredeposition properties. Granular detergent compositions whichcontain these compounds typically contain from about 0.01% to about10.0% by weight of the water-soluble ethoxylates amines; liquiddetergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898. Other groups of preferredclay soil removal-antiredeposition agents are the cationic compoundsdisclosed in EP 0111965 A1, the ethoxylated amine polymers disclosed inEP 0111984 A1, the zwitterionic polymers disclosed in EP 0112592 A1, andthe amine oxides disclosed in U.S. Pat. No. 4,548,744. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Graying Inhibitors

Graying inhibitors have the function of maintaining the dirt that wasremoved from the fibers suspended in the washing liquor, therebypreventing the dirt from resettling. Water-soluble colloids of mostlyorganic nature are suitable for this, for example, the water-solublesalts of (co)polymeric carboxylic acids, glue, gelatins, salts of ethercarboxylic acids or ether sulfonic acids of starches or celluloses, orsalts of acidic sulfuric acid esters of celluloses or starches.Water-soluble, acid group-containing polyamides are also suitable forthis purpose. Moreover, soluble starch preparations and others can beused as the above-mentioned starch products, e.g., degraded starches,aldehyde starches etc. Polyvinyl pyrrolidone can also be used.Preference, however, is given to the use of cellulose ethers such ascarboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkylcelluloses and mixed ethers such as methyl hydroxyethyl cellulose,methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose andmixtures thereof, as well as polyvinyl pyrrolidone, which can be added,for example, in amounts of 0.1 to 5 wt. %, based on the composition.

Optical Brighteners And UV Adsorbers

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from about 0.05% toabout 1.2%, by weight, into the detergent compositions herein.Commercial optical brighteners which can be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.

Preferred brighteners include the PHORWHITE® series of brighteners fromVerona. Other brighteners disclosed in this reference include: Tinopal®UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; ArticWhite® CC and Artic White CWD, available from Hilton-Davis; the2-(4-stryl-phenyl)-2H-napthol [1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(stryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2-d] oxazole; and2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. Anionic brighteners arepreferred herein.

The compositions may comprise e.g., derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof as the opticalbrighteners. Suitable optical brighteners are, for example, salts of4,4′-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonicacid or compounds of similar structure which contain a diethanolaminogroup, a methylamino group, an anilino group or a 2-methoxyethylaminogroup instead of the morpholino group. Brighteners of the substituteddiphenylstyryl type may also be present, for example, the alkali metalsalts of 4,4′-bis(2-sulfostyryl)diphenyl,4,4′-bis(4-chloro-3-sulfostyryl)diphenyl or4-(4-chlorostyryl)-4′-(2-sulfostyryl)diphenyl. Mixtures of the mentionedbrighteners may also be used.

In addition, UV absorbers may also be added. These are compounds withdistinct absorption abilities for ultra violet radiation, whichcontribute as UV stabilizers as well as to improve the light stabilityof colorants and pigments both for textile fibers as well as for theskin of the wearer of textile products by protecting against the UVradiation that penetrates the fabric. In general, the efficientradiationless deactivating compounds are derivatives of benzophenone,substituted with hydroxyl and/or alkoxy groups, mostly in position(s) 2and/or 4. Also suitable are substituted benzotriazoles, additionallyacrylates that are phenyl-substituted in position 3 (cinnamic acidderivatives), optionally with cyano groups in position 2, salicylates,organic Ni complexes, as well as natural substances such asumbelliferone and the endogenous urocanic acid. In a preferredembodiment, the UV absorbers absorb UV-A and UV-B radiation as well aspossible UV-C radiation and re-emit light with blue wavelengths, suchthat they additionally have an optical brightening effect. Preferred UVabsorbers encompass triazine derivatives, e.g.,hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine,o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole as well asbis(anilinotriazinyl-amino)stilbene disulfonic acid and theirderivatives. Ultra violet absorbing pigments like titanium dioxide canalso be used as UV absorbers.

Dye Transfer Inhibiting Agents

The detergent compositions of the present invention can also include oneor more materials effective for inhibiting the transfer of dyes from onefabric to another during the cleaning process. Generally, such dyetransfer inhibiting agents include polyvinyl pyrrolidone polymers,polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, manganese phthalocyanine, peroxidases, and mixturesthereof. If used, these agents typically comprise from about 0.01% toabout 10% by weight of the composition, preferably from about 0.01% toabout 5%, and more preferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein are described in U.S. Pat. No. 6,491,728, incorporated herein byreference.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as “PVNO”.

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as “PVPVI”) are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. The PVPVI copolymers typically have a molar ratio ofN-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, morepreferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.These copolymers can be either linear or branched.

The present invention compositions also can employ apolyvinylpyrrolidone (“PVP”) having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field. Compositions containingPVP can also contain polyethylene glycol (“PEG”) having an averagemolecular weight from about 500 to about 100,000, preferably from about1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppmbasis delivered in wash solutions is from about 2:1 to about 50:1, andmore preferably from about 3:1 to about 10:1.

The detergent compositions herein can also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

One preferred brightener is4,4′-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the trade name Tinopal-UNPA-GX® byCiba-Geigy

Corporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

Another preferred brightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the trade name Tinopal 5BM-GX® by Ciba-Geigy Corporation.

Another preferred brightener brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the trade name Tinopal AMS-GX® by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the “exhaustion coefficient”. The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric “brightness” benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Thickeners

The compositions can also comprise common thickeners and anti-depositioncompositions as well as viscosity regulators such as polyacrylates,polycarboxylic acids, polysaccharides and their derivatives,polyurethanes, polyvinyl pyrrolidones, castor oil derivatives, polyaminederivatives such as quaternized and/or ethoxylated hexamethylenediaminesas well as any mixtures thereof. Preferred compositions have a viscositybelow 10,000 mPa*s, measured with a Brookfield viscosimeter at atemperature of 20° C. and a shear rate of 50 min⁻¹.

Inorganic Salts

Further suitable ingredients of the composition are water-solubleinorganic salts such as bicarbonates, carbonates, amorphous silicates ormixtures of these; alkali carbonate and amorphous silicate areparticularly used, principally sodium silicate with a molar ratioNa₂O:SiO₂ of 1:1 to 1:4.5, preferably of 1:2 to 1:3.5. Preferredcompositions comprise alkaline salts, builders and/or cobuilders,preferably sodium carbonate, zeolite, crystalline, layered sodiumsilicates and/or trisodium citrate, in amounts of 0.5 to 70 wt. %,preferably 0.5 to 50 wt. %, particularly 0.5 to 30 wt. % anhydroussubstance.

Perfumes and Colorants

The compositions can comprise further typical detergent and cleansingcomposition ingredients such as perfumes and/or colorants, wherein suchcolorants are preferred that leave no or negligible coloration on thefabrics being washed. Preferred amounts of the totality of the addedcolorants are below 1 wt. %, preferably below 0.1 wt. %, based on thecomposition. The compositions can also comprise white pigments such ase.g., TiO₂.

INDUSTRIAL APPLICATION

Another object of the present invention refers to a method for improvingthe olfactory aspects and/or for preventing unpleasant olfactory aspectsof a fragrance, comprising the step of providing a fragrance in need ofolfactory support and applying at least one compound of formula (I) andat least one compound of formula (II) to said fragrance.

Finally, the invention also includes the use of the mixture ofcomponents (a), (b), (c) and optionally (d) for improving the olfactoryaspects and/or for preventing unpleasant olfactory aspects of afragrance

As far the method and the use is related to specific combinations ofspecies or their amounts reference is made to the explanations providedabove which are applicable mutatis-mutandis without repeating them.

EXAMPLES Example 1

121.6 g (−)-carveol (CAS 99-48-9), 30.8 g (−)-dihydrocarveol (CAS20549-47-7) and 3 g sodium carbonate were placed in a 2-l three-neckedflask equipped with KPG stirrer, dropping funnel and cooler anddissolved in 150 ml toluene. Subsequently, the mixture was heated andkept under reflux. Within one hour 112.2 g (1.1 mol) acetic anhydridewere added dropwise and the reaction continued for another two hours ata temperature of 120 ° C. Once esterification was terminated the productwas cooled down to about 75 to 80 ° C. and slowly subjected with 10 mlwater. The organic phase thus obtained was washed with portions of 50 mlwater, 50 ml sodium carbonate solution (5% b.w.) and sodium chloridesolution (5% b.w.). Finally, the organic phase was removed under vacuum(70 ° C., 15 mbar). The remaining solid essentially consisted of[(1R,5R)-5-isopropenyl-2-methyl-cyclohex-2-en-1-yl]acetate and[(1R,5R)-5-isoproepnyl-2-methyl-cyclohexyl]acetate in a ratio by weightof 82.5:17.5.

Example 2

The following mixtures A, B and C were obtained by blending thecomponents according to the following Table I.

TABLE I Fragrance compositions COMPOUNDS A B C AGRUNITRIL 1.54 0.00 1.54ALLYLCAPRONAT 0.03 0.00 0.03 AMYLSALICYLAT 0.01 0.00 0.01 BHT JONOL 0.100.00 0.10 CINEOL 1,4 0.04 0.00 0.04 CITRONELLOL 0.13 0.00 0.13CITRONELLYLACETAT 0.02 0.00 0.02 CORTEX ALDEHYD 50 0.01 0.00 0.01DIHYDROMYRCENOL 1.33 0.00 1.33 DIPROPYLENGLYCOL 0.83 0.00 0.83 EUGENOLNAT. 10% DPG 0.05 0.00 0.05 FENCHOL 10% DPG 0.01 0.00 0.01 FLOROPAL 0.020.00 0.02 GERANIOL 0.15 0.00 0.15 GERANYLACETAT 0.05 0.00 0.05HERBAFLORAT 0.67 0.00 0.67 HERBYLPROPIONAT 0.05 0.00 0.05 HEXYLACETAT0.67 0.00 0.67 KAMPFEROL 0.24 0.00 0.24 LINALOOL 0.72 0.00 0.72MANZANATE 0.02 0.00 0.02 METHYLHEPTENON-6,5,2 10% DPG 0.02 0.00 0.02NEROLIN BROMELIA 0.36 0.00 0.36 ORANGE 20X BASE 0.05 0.00 0.05ORANGENOEL BRAS. 0.46 0.00 0.46 STYROLYLACETAT 0.29 0.00 0.29 TERPINEOLALPHA 0.07 0.00 0.07 TERPINOLEN 0.62 0.00 0.62 VANILLIN 10% in DPG 0.150.00 0.15 GRAPEFRUITOL 1.28 0.00 1.28 PRODUCT ACCORDING EXAMPLE 1 0.000.02 0.02 DIPROPYLEMGLYCOL ad 100 ad 100 ad 100

Scent stripes were treated with the compositions A, B and C and scentintensity of certain olfactory aspects determined by a panel ofexperienced examiners using a scale from (0)=not to be detected to(10)=very strong. The results are compiled in Table II:

TABLE I Olfactory aspects ASPECTS A B C bloomy 5 0 7 fruity 3 0 5 amber4 0 7 ligneous 2 0 5 musky 1 0 4 metallic 3 4 0 oily 2 4 0 technical 4 30 onion-like 0 5 0 garlic-like 0 4 0 carbide 0 1 0

Formulation Examples 1 to 66

TABLE 1 Liquid soap. transparent (Amounts in % b.w.) Ingredients INCIName Amount Tagat O 2 PEG-20 Glyceryl Oleate 2.5 Coconut oildiethanolamine Cocamide DEA 5.0 condensate Abil B 8842 Cyclomethicone0.5 Sodium laurylethersulfate. 28% Sodium Laureth Sulfate 35.0Tego-Betaine L7 Cocamidopropyl Betaine 5.0 Soap. 25% Coconut acid.Potassium salt. 20.0 Potassium Oleate Fragrance composition B Fragrance0.4 Preservative DMDM Hydantoin 0.2 Water Water Ad 100

TABLE 2 Syndet soap. liquid (Amounts in % b.w.) Ingredients INCI NameAmount Elfan OS 46 Sodium Olefin C14-C16 Sulfonate 35.5 Armoteric LBLauryl Betaine 8.0 Elfan SG 10.0 Elfacos GT 282 L Talloweth-60 MyristylGlycol 3.0 PCL-Liquid 100 Cetearyl Ethylhexanoate 4.0 Fragrancecomposition B Fragrance 0.4 Preservative Methylchloroisothiazolinone.0.1 Methylisothiazinone Water Water Ad 100

TABLE 3 Cosmetic lotion for body wash (Amounts in % b.w.) IngredientsINCI Name Amount Lumerol K 28 Disodium Laureth Sulfosuccinate. 33.0Cocamidopropyl Betaine. Magnesium Lauryl Sulfate Amphotensid B 4Cocamidopropyl Betaine 10.0 Perlglanzmittel GM 4055 MIPA-Pareth-25Sulfate. 4.0 Glycol Stearate Sodium Chloride Sodium Chloride 2.0 Avocadooil Persea Gratissima (Avocado) Oil 3.0 Water Water Ad 100 Fragrancecomposition B Fragrance 0.5 Euxyl ® K727 Phenoxyethanol. Methyldibromo0.3 Glutaronitrile. Isothiazolinones

TABLE 4 Cosmetic lotion for body wash with Triclosan (Amounts in % b.w.)Ingredients INCI Name Amount Texapon N 25 Sodium Laureth Sulfate 37.5Lamepon S Potassium Cocoyl Hydrolyzed Collagen 28.0 Lamesoft LMGHydrogenated Tallow Glycerides. TEA- 5.0 Cocoyl Hydrolyzed CollagenLamesoft 156 Glyceryl Laurate. TEA-Cocoyl Hydrolyzed 5.0 Collagen SodiumChloride Sodium Chloride 1.7 Irgasan DP 300 Triclosan 0.5 Water Water Ad100 Fragrance Fragrance 0.3 composition B Euxyl ® K703 Phenoxyethanol.Benzoic Acid. 0.4 Dehydroacetic Acid

TABLE 5 Intimate wash (Amounts in % b.w.) Ingredients INCI Name AmountTegobetaine HS Cocamidopropyl Betaine. Glyceryl 15.0  Laurate Tagat L 2PEG-20 Glyceryl Laurate 2.0 Arlacide G Chlorhexidine Digluconate 0.1Rewoquat B 50 Benzalkonium Chloride 0.1 Lactic Acid. 80% Lactic Acid 0.1Water Water Ad 100 Fragrance composition B Fragrance 0.2 Euxyl ® K700Potassium Sorbate. Benzyl Alcohol. 0.3 Phenoxyethanol

TABLE 6 Liquid soap (Amounts in % b.w.) Ingredient INCI Amount Deionizedwater Water 2.0 Soap bases mix Sodium tallowates/palmitates 95.8Titanium dioxide Titanium dioxide 1.0 Fragrance composition B Fragrance1.2 Preservatives Phenoxyethanol 0.5 HydroxyacetophenoneHydroxyacetophenone 0.5

TABLE 7 Shampoo (Amounts in % b.w.) Ingredients Amount Sodium laurylether sulfate (e.g. Texapon NSO) 12 Cocamidopropyl betaine (e.g. DehytonK) 2 Sodium chloride 1.4 Citric acid 1.3 Fragrance composition B 0.3Phenoxyethanol. methyl-. ethyl-. butyl- and propylparaben 0.5 Water Ad100

TABLE 8 2-in-1 Shampoo (Amounts in % b.w.) Ingredients INCI Name AmountDeionized water Water Ad 100 Plantacare PS 10 Sodium Laureth Sulfate.20.0 Lauryl Glucoside Euperlan PK 771 Glycol Distearate. 6.0 SodiumLauryl Sulfate. Cocamide MEA. Laureth-10 Sodium chloride Sodium Chloride1.4 Citric acid monohydrate Citric acid 0.1 crystalline Fragrancecomposition B Fragrance 0.5 Dragocid Liquid Phenoxyethanol, Parabens 0.5Hydroxyacetophenone Hydroxyacetophenone 0.5

TABLE 9 Anti-dandruff Shampoo (Amounts in % b.w.) Ingredients AmountClimbazole 0.50 Sodium Laureth Sulfate 37.00 Cocamidopropyl Betaine 8.00PEG-6 Caprylic/Capric Glycerides 2.50 Laureth-2 2.00 Water (Aqua).Glycerol. Thymus Vulgaris (Thyme). 0.50 Flower/Leaf Extract Bisabolol0.10 Panthenol 0.50 Polyquaternium-10 0.40 Fragrance composition B 0.50Phenoxyethanol. Methylparaben. Ethylparaben. 0.70 Butylparaben.Propylparaben. Iso-butylparaben Water (Aqua) Ad 100

TABLE 10 Hair conditioner with Crinipan. rinse-off (Amounts in % b.w.)Ingredients INCI Name Amount Lanette ® O Cetearyl Alcohol 4.00 Dragoxat89 Ethylhexyl Isononanoate 2.00 Genamin ® KDM-P Behentrimonium Chloride1.00 SF 1550 Phenyl Trimethicone 0.10 Neo Heliopan ® BB Benzophenone-30.10 Crinipan ® AD Climbazole 0.80 Glycerol 99.5 P. Glycerol 6.00 WaterWater (Aqua) Ad 100 Actipone ® Alpha Pulp Water (Aqua). Butylene Glycol.Malic Acid. Actinidia 0.50 Chinensis (Kiwi) Fruit Juice. Citrus.Aurantium Dulcis (Orange). Juice. Citrus Paradisi (Grapefruit) Juice.Pyrus Malus (Apple) Juice. Trideceth-9. Prunus Amygdalus Dulcis (SweetAlmond) Seed Extract Extrapone ® Bamboo P Propylene Glycol. Water(Aqua). Butylene Glycol. 0.50 Bambusa Vulgaris Shoot Extract SodiumHydroxide 10% solution Sodium Hydroxide 0.40 Colour I Colour 0.60 ColourII Colour 0.30 Fragrance composition B Fragrance 0.40 PreservativeMethylparaben 0.20

TABLE 11 Sprayable hair conditioner with zinc pyrithrione. leave-on(Amounts in % b.w.) Ingredients INCI Name Amount Monomuls 60-35 CHydrogenated Palm Glycerides 1.70 Cetiol OE Dicaprylyl Ether 7.20 Abil100 Dimethicone 3.60 Dehyquart F 75 Distearoylethyl Hydroxyethylmonium.4.00 Methosulfate. Cetearyl Alcohol Eumulgin B1 Ceteareth-12 3.50 CetiolS Diethylhexylcyclohexane 7.20 D-Panthenol Panthenol 0.10 Glycerol 99.5P. Glycerol 1.50 Water Water (Aqua) Ad 100 Actipone ® Rosemary Water(Aqua). Propylene. Glycol. 0.10 Rosmarinus Officinalis. (Rosemary) LeafExtract Frescolat ® ML Cryst. Menthyl Lactate 0.50 Dragosantol100Bisabolol 0.10 Zinc Omadine Zinc pyrithione 0.10 Fragrance Fragrance0.40 composition B Phenonip ® phenoxyethanol. methylparaben. 0.30ethylparaben. butylparaben. propylparaben. isobutylparaben

TABLE 12 Hair conditioner with UV protection (Amounts in % b.w.)Ingredients INCI Name Amount Reflex PEG 6000 PEG-150 2.50 HairConditioner Base Cetyl alcohol. behentrimonium 3.00 chloride. TriticumVulgare (Wheat) bran extract. linoleic acid PCL-Solid Stearylheptanoate. stearyl 0.50 caprylate Dow Corning 5200 Laurylmethiconecopolyol 0.50 Natrosol 250 HR Hydroxyethylcellulose 0.50 Benzophenone-4Benzophenone-4 1.00 Neo Heliopan AP Disodiumphenyldibenz-imidazole 1.00tetrasulphonate Amino methyl propanol Amino methyl propanol 2.00 DowCorning 949 cationic Amodimethicone. cetrimonium 2.00 emulsion chloride.trideceth-12 Fragrance composition B Fragrance 0.80 1.2-hexanediol1.2-hexanediol 0.50 Hydroxyacetophenone Hydroxyacetophenone 0.50 WaterWater (Aqua) Ad 100

TABLE 13 Shower gel (Amounts in % b.w.) Ingredients INCI AmountDeionized water Water Ad 100 Plantacare PS 10 Sodium Laureth Sulfate.Lauryl 20.0 Glucoside Sodium chloride Sodium Chloride 1.4 Citric acidmonohydrate Citric Acid 1.3 crystalline Fragrance composition BFragrance 0.6 SymDiol ®68 1.2-hexanediol. caprylyl glycol 0.4

TABLE 14 Shaving foam (Amounts in % b.w.) Ingredients Amount Dem. Water77.2 Triethanolamine 4.0 Edenor L2 SM (Stearinic acid. Palmitinic acid)(Cognis) 5.3 Laureth-23 3.0 Stearylalcohol 0.5 Sodium lauryl sulfate 3.0Extrapone Seaweed (water. propylene glycol. potassium 1.0 iodide. FucusVesiculosus Extract) Dragosantol (Bisabolol. Farnesol) 0.1 Fragrancecomposition B 1.0 Euxyl ® K220 (Methylisothiazolinone.Ethylhexylglyerol) 0.6 Hydroxyacetophenone 0.3 Propane/Butane 4.2 Bar4.0

TABLE 15 Depilatory cream (Amounts in % b.w.) Ingredients AmountCetearyl alcohol 10.0 Ceteareth-12 2.0 PCL-Liquid(Cetearylethylhexanoate. Isopropylmyristate) 3.0 Dragosantol (Bisabolol.Farnesol) 0.1 Edenor L2 SM (Stearinic acid. Palmitinic acid) 1.0 Dem.Water 52.2 Urea 5.0 Dem. Water 10.0 Calcium thioglycolate 6.0 Sodiumhydroxide solution. 10% 10.0 Fragrance composition B 0.5 Neo DragocidPowder (Methyl parabene. sorbinic acid. 0.2 Dehydro acetic acid. Propylparabene) Hydroxyacetophenone 0.4

TABLE 16 After Shave Tonic (Amounts in % b.w.) Ingredients INCI AmountSymSol ® PF-3 Water (Aqua). Pentylene Glycol. 3.00 Sodium LaurylSulfoacetate. SodiumOleoyl Sarcosinate. Sodium Chloride. DisodiumSulfoacetate. SodiumOleate. Sodium Sulfate SymSitive ® 1609 PentyleneGlycol. 4-t-Butyl- 1.00 cyclohexan ol Frescolat ® ML Menthyl Lactate0.30 Glycerol 99.5 P. Glycerol 5.00 Water Water (Aqua) Ad 100Extrapone ® Glacier Water Glycerol. Water (Aqua) 1.00 GW SymCalmin ®Butylene Glycol. Pentylene Glycol. 0.50 Hydroxyphenyl PropamidobenzoicAcid Dragosine ® Carnosine 0.10 Hydrolite ® 5 Pentylene Glycol 5.00Ethanol 96% Alcohol Denat. 5.00 Colour Pigment Colour Pigment 0.05Fragrance composition B Fragrance 0.15

TABLE 17 Deodorant formulation in the form of a roll-on gel (Amounts in% b.w.) Ingredients Amount 1.3-butylene glycol 2.00 PEG-40-hydrogenatedcastor oil 2.00 Hydroxyethylcellulose 0.50 Fragrance composition B 0.301.3-propanediol 0.50 3-phenylpropanol 0.40 Ethylhexyl glycerin 0.10Water ad 100.00

TABLE 18 Clear deo anti-perspirant roll-on (Amounts in % b.w.)Ingredients INCI Amount Methocel E4M Premium HydroxypropylMethylcellulose 0.50 Water Water (Aqua) Ad 100 Neo-PCL WaterTrideceth-9. PEG-5 Ethylhexanoate. 1.00 Soluble N Water (Aqua)Solubilizer PEG-40 Hydrogenated Castor Oil. 3.00 Trideceth-9. PropyleneGlycol. Water (Aqua) Deolite Dimethyl Phenylpropanol. Pentylene 0.50Glycol Locron LW Aluminium Chlorohydrate 25.00 Aloe Vera Gel AloeBarbadensis Leaf Juice 1.00 Concentrate 10/1 Propylene Glycol-1.2Propylene Glycol 4.00 99 P GC Ethanol 96% Alcohol Denat. 30.00 Fragrancecomposition B Fragrance 1.00

TABLE 19 Deodorant stick (Amounts in % b.w.) Ingredients Amount Sodiumstearate 8.00 PPG-3 Myristyl ether 70.00 1.2-propylene glycol 10.001.1-dimethyl-3-phenylpropanol 0.20 2-butyloctanoic acid 0.20 Fragrancecomposition B 0.60 Heptoxy-1.2-propanediol 0.20 Phenoxyethanol 0.30Water Ad 100

TABLE 20 Zirconium suspensoid antiperspirant stick (Amounts in % b.w.)Ingredients INCI Amount PCL Liquid 100 Cetearyl ethylhexanonate to 100Silicone Fluid 345 Cyclomethicone 10.00 CRODACOL C90 Cetyl Alcohol 8.00SYNCROWAX HGLC C18-36 Triglyceride 8.00 CRODAMOL PTC PentaerythritolTetracaprylate/Caprate 5.00 SYNCROWAX HRC Tribehenin 4.00 VOLPO N5Oleth-5 1.00 Titanium Dioxide 1.00 Rezal 36GP AluminiumTetrachlorohydrex GLY 20.00 Dry Flo C Aluminium Starch Octenyl Succinate22.50 Fragrance composition B Fragrance 0.60 Preservative Phenoxyethanol0.40 Hexoxy-1.2-propanediol 0.10 Substance of formula (I)Hydroxyacetophenone 0.40

TABLE 21 Deodorant pump spray with SymClariol (Amounts in % b.w.)Ingredients INCI Amount SymClariol ® Decylene Glycol 0.50 SolubilizerPEG-40 Hydrogenated Castor Oil. 4.00 Trideceth-9. Propylene Glycol.Water (Aqua) Neo-PCL Water Soluble Trideceth-9. PEG-5 Ethylhexanoate.1.50 N Aqua SymRelief ® Bisabolol. Zingiber Officinale 0.10 (Ginger)Root Extract Water Water (Aqua) Ad 100 1.2 Propylene Glycol PropyleneGlycol 6.00 Fragrance composition B Fragrance 0.40 SymDiol ® 681.2-Hexanediol. Caprylyl Glycol 0.20

TABLE 22 Antiperspirant formulations (Amounts in % b.w.) IngredientsAmounts Reach AZP-908 SUF 24.00 Cyclomethicone (Pentamer) Ad 100Polydecene (Silkflo 364 NF) 17.50 Neo Heliopan OS (ethylhexylsalicylate) 2.50 L-Menthyl lactate (Frescolate ML) 0.25 Polyethylene3.00 Hydrogenated castor oil 2.00 Promyristyl PM-3 7.00 PEG-8 Distearate3.00 Silicon dioxide (Cab-O-Sil M-5) 1.00 Stearyl alcohol 15.00Octyldodecanol 0.10 Fragrance composition B 0.80 3-Phenylpropanol 0.40Substance of formula (I) 0.60

TABLE 23 Deodorant spray with Triclosan (Amounts in % b.w.) IngredientsAmount PEG-40-hydrogenated castor oil 3.00 Ethylhexylglycerol(Octoxyglycerol) 0.80 Ethanol 40.00  Citrate buffer 0.501.2-Hexanediol/1.2-octanediol (1:1) — Triclosan ®(5-chloro-2-(2.4-dichlorophenoxy)phenol) 0.25 2-Benzylheptan-1-ol(Jasmol) — Fragrance composition B 0.75 Phenoxyethanol 0.40 Water Ad 100

TABLE 24 O/W lotion (Amounts in % b.w.) Ingredients Amount Paraffin oil5.00 Isopropyl palmitate 5.00 Cetyl alcohol 2.00 Beeswax 2.00Ceteareth-20 2.00 PEG-20-glyceryl stearate 1.50 Glycerol 3.00 Fragrancecomposition B 0.30 Methylparaben 0.30 Water ad 100.00

TABLE 25 Body lotion (Amounts in % b.w.) Ingredients Amount CetearylAlcohol 2.00 Ethylhexyl Isononanoate 5.00 Cetearyl Ethylhexanoate.Isopropyl Myristate 3.00 Glyceryl Oleate Citrate. Caprylic/CapricTriglyceride 4.00 Water (Aqua) 79.50 Carbomer 0.30 Sodium Benzoate 0.100Propylene Glycol 5.00 Sodium Hydroxide 30% solution 0.30 Fragrancecomposition B 0.30 Triethylene Glycol. Imidazolidinyl Urea.Methylparaben. 0.30 Propylparaben. Dehydroacetic AcidHydroxyacetophenone 0.20

TABLE 26 Cream (Amounts in % b.w.) Ingredients Amount Paraffin oil10.00  Ozokerite 4.00 Vaseline 4.00 Vegetable oil 10.00  Wool waxalcohol 2.00 Aluminium stearate 0.40 Fragrance composition B 0.701.2-pentanediol 2.00 Phenoxyethanol 0.50 Water ad 100.00

TABLE 27 Cream (Amounts in % b.w.) Ingredients INCI Amount Dracorin ® CEGlyceryl Stearate Citrate 1.00 Lanette ® O Cetearyl Alcohol 2.00Cutina ® GMS-V Glyceryl Stearate 1.00 Tegosoft ® MM Myristyl Myristate1.00 Xiameter ® PMX-0246. Cyclosiloxane Cyclohexasiloxane (and)Cyclopentasiloxane 0.50 Dragoxat ® 89 Ethylhexyl Isononanoate 2.00PCL-Liquid 100 Cetearyl Ethylhexanoate 4.00 Neutral Oil Caprylic/CapricTriglyceride 4.00 Carbopol ® Ultrez 21 Acrylates/C10-30 Alkyl AcrylateCrosspolymer 0.20 Keltrol ® CG-T Xanthan Gum 0.10 Water Water (Aqua) Ad100 Glycerol 99.5 P. Glycerol 3.00 Propylene Glycol-1.2 99 P GCPropylene Glycol 2.00 Sodium Benzoate Sodium Benzoate 0.10 SodiumHydroxide 10% solution Sodium Hydroxide 0.50 Fragrance composition BPerfume 0.30 Euxyl ® K702 Dehydroacetic Acid. Benzoic Acid. Phenoxy-0.30 ethanol. Polyaminopropyl Biguanide. Ethylhexyl- glycerin4-hydroxyacetophenone Hydroxyacetophenone 0.70

TABLE 28 Hand and body cream (Amounts in % b.w.) Ingredients INCI AmountDracorin ® GOC Glyceryl Oleate Citrate. Caprylic/Capric Triglyceride2.00 PCL-Solid Stearyl Heptanoate. Stearyl Caprylate 2.50 Lanette ® OCetearyl Alcohol 1.50 Cutina ® GMS-V Glyceryl Stearate 1.00 Dragoxat ®89 Ethylhexyl Isononanoate 3.00 PCL-Liquid 100 Cetearyl Ethylhexanoate7.00 Isodragol ® Triisononanoin 4.00 Xiameter ® PMX-0345 CyclosiloxaneCyclopentasiloxane (and) Cyclohexasiloxane 0.50 Water Water (Aqua) Ad100 Carbopol ® Ultrez 21 Acrylates/C10-30 Alkyl Acrylate Crosspolymer0.20 Keltrol ® CG-RD Xanthan Gum 0.10 Glycerol 85 P. Glycerol 3.00DragoBetaGlucan Water (Aqua). Butylene Glycol. Glycerol. Avena 1.50Sativa (Oat) Kernel Extract Potassium Sorbat Potassium Sorbate 0.10Sodium Hydroxide 10% solution Sodium Hydroxide 0.50 Fragrancecomposition B Parfum 0.20 Euxyl ® K300 Methyl-. Butyl-. Ethyl-. Propyl.Isobutylparaben. 0.30 Phenoxyethanol. 4-HydroxyacetophenoneHydroxyacetophenone 0.30

TABLE 29 Face cream (Amounts in % b.w.) Ingredients INCI AmountEmulsiphos ® Potassium Cetyl Phosphate. Hydrogenated Palm 1.50Glycerides Cutina ® GMS-V Glyceryl Stearate 1.70 Lanette ® O CetearylAlcohol 3.00 Tegosoft ® MM Myristyl Myristate 1.00 PCL-Liquid 100Cetearyl Ethylhexanoate 1.00 Isodragol ® Triisononanoin 3.00 Dragoxat ®89 Ethylhexyl Isononanoate 4.00 Avocado Oil Persea Gratissima (Avocado)Oil 3.00 Abil ® 350 Dimethicone 0.50 Covi-ox ® T-70 Tocopherol 0.10Edeta ® BD Disodium EDTA 0.10 Carbopol ® Ultrez 21 Acrylates/C10-30Alkyl Acrylate Crosspolymer 0.30 Keltrol ® CG-RD Xanthan Gum  0.150Water Water (Aqua) Ad 100 Glycerol 99.5 P. Glycerol 4.00 PropyleneGlycol-1.2 99 P GC Propylene Glycol 3.00 SymMatrix ® Maltodextrin. RubusFruticosus (Blackberry) Leaf 0.50 Extract Sodium Hydroxide 10% solutionSodium Hydroxide 0.50 Fragrance composition B Parfum 0.30 Euxyl ® K712Sodium Benzoate. Potassium Sorbate 0.20 4-HydroxyacetophenoneHydroxyacetophenone 0.60

TABLE 30 Moisturizing body care cream (Amounts in % b.w.) IngredientAmount PEG-7 hydrogenated castor oil 6.00 Cetearyl ethyl hexanoate 10.00Isopropyl myristate 5.00 Mineral oil 7.00 Shea Butter (Butyrospermumparkii) 0.50 Aluminum stearate 0.50 Magnesium stearate 0.50 Bisabolol0.20 Quaternium-18-Hectorit 0.70 Dipropylene glycol 5.0 Magnesiumsulfate 0.70 Pentylene glycol 4.00 Fragrance composition B 0.30Preservative (Phenoxyethanol) 0.20 Hydroxyacetophenone 0.40 Aqua dem.58.90

TABLE 31 Anti-wrinkle cream (Amounts in % b.w.) Ingredients AmountGlyceryl Stearate Citrate 1.00 Glyceryl Laurate 1.00 Cetearyl Alcohol(and) Myristyl Myristate 3.00 Cetearyl Ethylhexanoate 4.00 Mineral oil4.00 Cyclopentasiloxane/Cyclohexasiloxane 0.50 Acrylates/C10-30 AlkylAcrylate Crosspolymer 0.20 Water Ad 100 1.2-Hexanediol 2.00 SodiumHydroxide 10% solution 0.10 Narcissus Tazetta Bulb Extract 1.00Fragrance composition B 0.30 Preservative (Phenoxyethanol) 0.50

TABLE 32 Functional skin oil for disinfection (Amounts in % b.w.)Ingredients INCI Amount Neutral Oil Caprylic/Capric Triglyceride Ad 100Sweet Almond Oil Prunus Dulcis 20.00 Dragoxat ® 89 EthylhexylIsononanoate 4.00 Isopropyl Palmitate Isopropyl Palmitate 6.00PCL-Liquid 100 Cetearyl Ethylhexanoate 15.00 Dragosantol ® 100 Bisabolol0.20 Retinyl Acetate In Oil (1 Mio. le/G) Retinyl Acetate 0.50 Vitamin EAcetate Tocopheryl Acetate 0.50 Covi-ox ® T-70 Tocopherol 0.10 Fragrancecomposition B Parfum 0.30 Preservative Methyl-. Butyl-. Ethyl-.Propylparaben 0.30 4-hydroxyacetophenone Hydroxyacetophenone 0.40

TABLE 33 Septic wound cream (Amounts in % b.w.) Ingredients (INCI)Amount Sorbitan Isostearate. Hydrogenated Castor Oil. 6.00 Ceresin.Beeswax (Cera Alba) Petrolatum 21.00 Cera Alba 5.00 Cetearyl Alcohol7.00 Prunus Dulcis 7.00 Lanolin 5.00 Paraffinum Liquidum 12.00 Fragrancecomposition B 0.30 Water (Aqua) Ad 100 Panthenol 7.00 Magnesium Sulfate0.70 Pentylene Glycol 1.00 Tocopheryl Acetate 1.00 Octenidinedihydrochloride 0.10 Phenoxyethanol 0.50

TABLE 34 Moisturizing and disinfecting face mask (Amounts in % b.w.)Ingredients INCI Amount Water Water (Aqua) Ad 100 Stabileze QM PVM/MaDecadiene Crosspolymer 0.50 Biotive ® L-Arginine Arginine 0.75Actipone ® Laminaria Saccharina GW Glycerol. Water (Aqua). LaminariaSaccharina 1.00 Extract Extrapone ® Cucumber Water (Aqua). PropyleneGlycol. Cucumis Sativus 1.00 (Cucumber) Juice Glycerol 99.5 P. Glycerol7.00 Neo Actipone ® Soap Nutshell Sapindus Mukurossi Peel Extract 0.50Colour I Colour 0.01 Hydrolite ® 5 Pentylene Glycol 5.00 SolubilizerPEG-40 Hydrogenated Castor Oil. Trideceth-9. 0.60 Water (Aqua) Fragrancecomposition B Parfum 0.08 Preservative Phenoxyethanol 0.404-hydroxyacetophenone Hydroxyacetophenone 0.40

TABLE 35 Sprayable disinfecting gel (Amounts in % b.w.) Ingredients INCIAmount Water Water (Aqua) Ad 100 Stabileze QM PVM/Ma DecadieneCrosspolymer 0.25 Sodium Hydroxide Sodium Hydroxide 0.40 10% solutionCoffein pure Caffeine 0.50 Extrapone ® Propylene Glycol. Water (Aqua).Glucose. 1.00 Horse Chestnut Aesculus Hippocastanum (Horse Chestnut)Seed Extract. Lactic Acid Hydrolite ® 5 Pentylene Glycol 3.00 1.3Butylene Glycol Butylene Glycol 5.00 Biotive ® Esculin Esculin 0.30Sesquihydrate Ethanol 96% Alcohol Denat. 10.00 Solubilizer PEG-40Hydrogenated Castor Oil. 0.50 Trideceth-9. Water (Aqua) Fragrance Parfum0.20 composition B Octenidine 0.10 dihydrochloride PreservativePhenoxyethanol 0.70 4-hydroxy- Hydroxyacetophenone 0.30 acetophenone

TABLE 36 Mineral wash and cleaning gel (Amounts in % b.w.) IngredientsINCI Amount Water Water (Aqua) Ad 100 Pionier ® NP Sodium Carbomer 1.5037 G SymSol ® Water (Aqua). Pentylene Glycol. Sodium 5.00 PF-3 LaurylSulfoacetate. SodiumOleoyl Sarcosinate. Sodium Chloride. DisodiumSulfoacetate. SodiumOleate. Sodium Sulfate Hydroviton ® Water (Aqua).Pentylene Glycol. Glycerol. 1.00 24 Sodium Lactate. Lactic Acid. Serine.Urea. Sorbitol. Sodium Chloride. Allantoin Extrapone ® Water (Aqua).Glycerol. Hydrolyzed Silk 1.00 Silk GW Hydrolite ® 5 Pentylene Glycol4.00 Actipearls Water (Aqua). Propylene Glycol. Algin. 1.00 Red Star #Gellan Gum. Xanthan Gum. CalciumChloride. DH10402/6 CI 12490 (PigmentRed 5). Mica (CI 77019). Titanium Dioxide (CI 77891) Fragrance Parfum0.50 composition B 3-Phenyl- 0.70 propanol 4-hydroxy-Hydroxyacetophenone 0.30 acetophenone

TABLE 37 Anti-acne wash (Amounts in % b.w.) Ingredients (INCI) AmountWater (Aqua) 45.70 Polyquaternium-7 0.50 Cocamidopropyl Betaine 9.0009.00 Coco Glucoside 2.000 2.00 Polysorbate 80. Glycerol. GossypiumHerbaceum. 1.00 (Cotton) Seed Oil. Water (Aqua) Trideceth-9. PEG-5Ethylhexanoate. Water (Aqua) 1.00 Glycereth-90 Isostearate. Laureth-20.50 Sodium Laureth Sulfate 37.000 37.00 Glycerol. Triticum Vulgare(Wheat) Gluten. 1.00 Water (Aqua) Sodium Chloride 0.30 Fragrancecomposition B 1.00 Phenoxyethanol. Methylparaben. Ethylparaben.Butylparaben. 0.30 Propylparaben. Isobutylparaben Substance of formula(I) 0.50

TABLE 38 Cosmetic sun protection composition (Amounts in % b.w.)Ingredient Amount Ethylhexyl cinnamic acid 7.50 Benzophenon-3 2.00Polyglyceryl dimer soyate 0.80 Sorbitane stearate 1.00 Tocopherylacetate 0.50 Glyceryl stearate. PEG-100 Stearate 3.00 PEG-40.hydrogenated castor oil 1.00 Titanium dioxide. aluminum oxide hydrate.3.00 Dimethicon/Methicon Copolymer Butyrospermum parkii (Shea Butter)1.00 C₁₂₋₁₅ alkyl benzoate 6.50 Butylene glycol 5.00 Xanthan gum 0.30Disodium EDTA 0.10 Allantoin 0.10 Polyacryl amide. C₁₃₋₁₄ isoparaffin.1.00 Laureth-7 Pentylene glycol 5.00 4-t Butylcyclohexanol 1.00Fragrance composition B 0.30 Preservatives (Methyl-. Butyl-. Ethyl-.Propylparaben. 0.30 Phenoxyethanol) Substance of formula (I) 0.60 Aquadem. Ad 100

TABLE 39 Sun protection spray (Amounts in % b.w.) Ingredients INCIAmount Water. demineralized Water (aqua) 69.50 Glycerol Glycerol 4.001.3 butylene glycol Butylene glycol 5.00 D-Panthenol Panthenol 0.50 LaraCare A-200 Galactoarabinan 0.25 Baysilone oil M 10 Dimethicone 1.00Edeta BD Disodium EDTA 0.10 Copherol 1250 Tocopheryl acetate 0.50 CetiolOE Dicaprylyl ether 3.00 Neo Heliopan ® HMS Homosalate 5.00 NeoHeliopan ® AV Ethylhexyl methoxycinnamate 6.00 Neo Heliopan ® 357 Butylmethoxydibenzoylmethane 1.00 Corapan TQ Diethylhexylnaphthalate 2.00Alpha Bisabolol Bisabolol 0.10 Pemulen TR-2 Acrylates/C10-30 alkylacrylate 0.25 crosspolymer NaOH. 10% Sodium hydroxide 0.60 Fragrancecomposition Fragrance 0.20 B Phenoxyethanol Phenoxyethanol 0.40 SolbrolM Methylparaben 0.10 Solbrol P Propylparaben 0.10 4-hydroxy-Hydroxyacetophenone 0.50 acetophenone

TABLE 40 Sunscreen spray O/W. SPE 15-20 (Amounts in % b.w.) IngredientsINCI Amount Dracorin ® GOC Glyceryl Oleate Citrate. 2.00 Caprylic/CapricTriglyceride Corapan ® TQ Diethylhexyl 2.6-Naphthalate 3.00 NeoHeliopan ® HMS Homosalate 7.00 Neo Heliopan ® OS Ethylhexyl Salicylate5.00 Neo Heliopan ® 357 Butyl Methoxydibenzoylmethane 3.00 IsoadipateDiisopropyl Adipate 6.00 Baysilone ® Oil M10 Dimethicone 1.00 Edeta ® BDDisodium EDTA 0.10 Vitamin E Acetate Tocopheryl Acetate 0.50Dragosantol ® 100 Bisabolol 0.10 Pemulen ® TR-2 Acrylates/C10-30 AlkylAcrylate 0.25 Crosspolymer Water Water (Aqua) Ad 100 Glycerol 99.5 P.Glycerol 4.00 Butylene Glycol Butylene Glycol 5.00 Neo Heliopan ® HydroPhenylbenzimidazole Sulfonic 8.00 (103089). used as 25% aq. Acidsolution neutralized with Biotive ® L-Arginine Biotive ® L-ArginineArginine 0.55 Fragrance composition B Fragrance 0.40 Sobrol MMethylparaben 0.30 4-hydroxy- Hydroxyacetophenone 0.60 acetophenone

TABLE 41 Sun protection soft cream (W/O). SPF 40 (Amounts in % b.w.)Ingredients INCI Amount Dehymuls PGPH Polyglyceryl-2 5.00dipolyhydroxystearate Copherol 1250 Tocopheryl acetate 0.50 Permulgin3220 Ozocerite 0.50 Zinc stearate Zinc stearate 0.50 Tegosoft TN C12-15Alkyl benzoate 10.00  Neo Heliopan ® E1000 Isoamyl-p-methoxycinnamate2.00 Neo Heliopan ® 303 Octocrylene 5.00 Neo Heliopan ® MBC4-Methylbenzylidene camphor 3.00 Zinc oxide. neutral Zinc oxide 5.00Water. distilled Water (aqua) Add 100 EDETA BD Disodium EDTA 0.10Glycerol Glycerol 4.00 Magnesium sulfate Magnesium sulfate 0.50Fragrance composition B Parfum 0.30 Symdiol ® 68 1.2-Hexanediol.Caprylylglycol 0.30 Substance of formula (I) 0.80

TABLE 42 Sun protection milk (W/O) (Amounts in % b.w.) Ingredients INCIAmount Dehymuls PGPH Polyglyceryl-2 3.00 dipolyhydroxystearate Beeswax8100 Beeswax 1.00 Monomuls 90-0-18 Glyceryl oleate 1.00 Zinc stearateZinc stearate 1.00 Cetiol SN Cetearyl isononanoate 5.00 Cetiol OEDicaprylyl ether 5.00 Tegosoft TN C12-15 alkyl benzoate 4.00 Vitamin ETocopherol 0.50 Neo Heliopan ® OS Ethylhexyl salicylate 5.00 NeoHeliopan ® AV Ethylhexyl methoxycinnamate 7.50 Uvinul ® T150 Ethylhexyltriazone 1.50 Water. distilled Water (Aqua) To 100 Trilon BD DisodiumEDTA 0.10 Glycerol Glycerol 5.00 Neo Heliopan ® AP 10% Disodium phenyldibenzimidazole 15.00 solution. neutralized tetrasulfonate with NaOHFragrance composition B Parfum 0.25 Alpha bisabolol Bisabolol 0.10SymOcide ® PT Phenoxyethanol. Tropolone 0.25 4-hydroxyacetophenoneHydroxyacetophenone 0.25

TABLE 43 After sun gel (Amounts in % b.w.) Ingredients INCI AmountSymSol ® PF-3 Water (Aqua). Pentylene Glycol. Sodium 3.000 LaurylSulfoacetate. SodiumOleoyl Sarcosinate. Sodium Chloride. DisodiumSulfoacetate. SodiumOleate. Sodium Sulfate Glycerol 99.5 P. Glycerol5.000 SymHelios ® 1031 Benzylidene Dimethoxydimethylin danone 0.100Water Water (Aqua) Ad 100 Pemulen ® TR-2 Acrylates/C10-30 Alkyl Acrylate1.000 Crosspolymer D-Panthenol 75 W Panthenol 0.500 SymFinity ® 1298Echinacea Purpurea Extract 0.100 Extrapone ® Pearl Water (Aqua).Glycerol. Hydrolyzed 1.000 GW Pearl. Xanthan Gum Sodium Hydroxide SodiumHydroxide 2.500 10% solution Ethanol 96% Alcohol Denat. 15.000 FragranceParfum 0.20 composition B SymOcide ® PS Phenoxyethanol. 1.2-Hexanediol.0.50 Decyleneglycol 4-hydroxy- Hydroxyacetophenone 0.50 acetophenone

TABLE 44 After sun lotion (Amounts in % b.w.) Ingredients AmountAcrylate/C10-30 alkylacrylate crosspolymer 0.4 Cetearylethyl hexanoate15.0 Bisabolol 0.2 Tocopheryl acetate 1.0 Panthenol 1.0 Alcohol 15.0Glycerol 3.0 Fragrance composition B 0.30 1.2-Hexanediol 0.60Hydroxyacetone 0.30 Pentylene glycol 4.0 Aqua dem. Ad 100Triethanolamine 0.2

TABLE 45 Hair styling gel (Amounts in % b.w.) Ingredients Amount WaterAd 100 PVM/MA Decadiene Crosspolymer 0.60 PVP 3.00 Isocetyl Stearate4.00 Ethylhexyl Methoxycinnamate 0.50 Aminomethyl Propanol 0.40Fragrance composition B 0.60 SymDiol ® 68T (1.2-Hexanediol.1.2-Octanediol. Tropolone) 0.30 Phenoxyethanol 0.20 Hydroxyacetophenone0.40

TABLE 46 Silicone emulsion (Amounts in % b.w.) Ingredients AmountPotassium Cetyl Phosphate. Hydrogenated Palm Glycerides 1.00Cyclohexasiloxane 4.00 Cetearyl Alcohol 1.50 Phenyl Trimethicone 3.00Stearyl Heptanoate. Stearyl Caprylate 3.00 Dimethicone 1.00 Xanthan Gum0.20 Isoamyl p-Methoxycinnamate 5.00 Water Ad 100 Methylpropanediol 3.00Fragrance composition B 0.30 Diazolidinyl urea 0.10

TABLE 47 Microemulsion gel (Amounts in % b.w.) Ingredient AmountGlycerol isostearate 1.80 Octoxyglycerol 1.00 Ceteareth-15 5.20 PEG-150Distearate 1.00 Aluminium chlorohydrate 5.00 Isotridecylisononanoate3.30 Cyclomethicone 6.60 Fragrance composition B 0.70 Euxyl ® K145(Methylchloroisothiazolinone. 0.10 Methylisothiazlinone. Bronopol)Hydroxyacetophenone 0.40 Water Ad 100

TABLE 48 Air freshener in gel form (Amounts in % b.w.) Ingredient AmountDemineralised water Ad 100 Genugel ® X-6424 (carrageenan) 2.00 Arkopal ®N 100 or Tergitol ® NP 10 (Emulsifer) 3.50 Fragrance composition B 0.60Preventol ® D 7 (5-chloro-2-methyl-4-isothiazolin-3-one. 0.102-methyl-2H isothiazol-3-one) Substance of formula (I) 0.80

TABLE 49 Cleaner. APC liquid. alkaline pH 8-10 (Amounts in % b.w.)Ingredients (INCI) Amount Aqua 59.06 Tri Sodium Citrate Dihydrate 3.00Sodium Laureth Sulfate 30.00 Trideceth-9 5.00 Ethanol 2.00 Citric Acid10% solution 0.24 Fragrance composition B 0.50 Mixture of5-Chloro-2-methyl-2H-isothiazol-3-one 0.10 and2-Methyl-2H-isothiazol-3-one Hydroxyacetophenone 0.30

TABLE 50 Fabric softener (Amounts in % b.w.) Ingredients (INCI) AmountAqua 72.10 Dialkylester ammomium methosulfate 16.60 Polydimethylsiloxane0.30 Magnesiumchloride 10.00 Perfume oil P1. P2. P3 or P4 0.60 Mixtureof 5-Chloro-2-methyl-2H-isothiazol-3-one and 0.102-Methyl-2H-isothiazol-3-one Hydroxyacetophenone 0.40

TABLE 51 Liquid detergent (Amounts in % b.w.) Ingredients AmountDeionized water 39.60 Optical brightener 0.10 Coconut fatty acids(C12-C18) 7.50 Potassium hydroxide 50% solution 4.30 Propane-1.2-diol5.00 Fatty alcohols C12-C15. 8 EO 12.00 Na-salt of secondary alkylsulfonates (C13-C17) 17.00 Triethanolamine 2.00 Trisodium citratedihydrate 5.00 Dequest 2066 Diethylenetriamine penta(methylenephosphonic 3.00 acid) Ethanol 3.00 Enzymes 0.70 Fragrance composition B0.50

TABLE 52 Liquid detergent concentrate (Amounts in % b.w.) IngredientsAmount Deionized water 12.9 Coconut fatty acids (C12-C18) 10.0 Fattyalcohols C12-C15. 8 EO 26.0 Na-salt of secondary alkyl sulfonates(C13-C17) 26.5 Triethanol amine 8.5 Na-salt of fatty alcohol sulfatesC12-C14 3.0 Ethanol 5.5 Urea 4.5 Enzymes 0.9 Citric acid 1.0 Fragrancecomposition B 0.7 Hydroxyacetophenone 0.8

TABLE 53 Solution for wet wipes (Amounts in % b.w.) Ingredients INCIAmount SymSol ® PF-3 Water (Aqua). Pentylene Glycol. Sodium Lauryl 2.00Sulfoacetate. SodiumOleoyl Sarcosinate. Sodium Chloride. DisodiumSulfoacetate. SodiumOleate. Sodium Sulfate Dragosantol ® 100 Bisabolol0.10 Glycerol 99.5 P. Glycerol 5.00 Water Water (Aqua) Ad 100Hydrolite ® 5 Pentylene Glycol 5.00 D-Panthenol 75 W Panthenol 0.80DragoCalm ® Water (Aqua). Glycerol. Avena Sativa (Oat) 1.00 KernelExtract Witch Hazel-Distillate Hamamelis Virginiana (Witch Hazel) Water.1.00 Water (Aqua). Alcohol Allplant Essence ® Org. PelargoniumGraveolens Flower/Leaf/Stem 1.00 Rose Geranium P Water Fragrancecomposition B Parfum 0.10 Preservative Phenoxyethanol 0.304-hydroxyacetophenone Hydroxyacetophenone 0.50

TABLE 54 Toothpaste (Amounts in % b.w.) Ingredients Amount Water(deionized) Ad 100 Sorbitol 70% 45.00 Trisodiumphosphate 0.10 Saccharin0.20 Sodiummonofluorophosphate 1.14 PEG 1500 5.00 Sident 9 (abrasivesilica) 10.00 Sident 22 S (Thickening silica) 8.00Sodiumcarboxymethylcellulose 1.10 Titanium (IV) oxide 0.50 Water(deionized) 4.50 Sodiumlaurylsulfate (SLS) 1.50 Fragrance composition B1.00 Solbrol M (Sodium salt) (Methylparaben) 0.15 Hydroxyacetophenone0.40

TABLE 55 Toothpaste with zinc citrate (Amounts in % b.w.) IngredientsAmount Water (deionized) Ad 100 Sorbitol 70% 45.00 Trisodiumphosphate0.10 Saccharin 0.20 Sodiummonofluorophosphate 1.14 PEG 1500 5.00 Sident9 (abrasive silica) 10.00 Sident 22 S (Thickening silica) 8.00Sodiumcarboxymethylcellulose 1.10 Zinc citrate 1.00 Titanium (IV) oxide0.50 Water (deionized) 4.50 Sodiumlaurylsulfate (SLS) 1.50 Fragrancecomposition B 1.00 SymDiol ® 68 (1.2-Hexanediol. Caprylylglycol) 0.25Hydroxyacetophenone 0.10

TABLE 56 Mouth rinse (Amounts in % b.w.) Ingredients Amount Ethylalcohol10.00 Cremophor CO 40 (PEG 40 hydrogenated castor oil) 1.00 Fragrancecomposition B 0.25 Water (deionized) To 100.00 Sorbitol 70% 5.00Sodiumsaccharin 450 0.07 Sodiumfluoride 0.18 Benzoic acid 0.12Hydroxyacetophenone 0.30

TABLE 57 Gel dental cream (Amounts in % b.w.) Ingredients Amount Nacarboxymethylcellulose 0.40 Sorbitol 70%. in water 72.00 Polyethyleneglycol (PEG) 1500 3.00 Na saccarinate 0.07 Na fluoride 0.24 Fragrancecomposition B 1.00 Abrasive silica 11.00 Thickening silica 6.00 Sodiumdodecyl sulfate (SDS) 1.40 Dist. water Ad 100 p-Hydroxybenzoic acid(PHB) ethyl ester 0.15 4-hydroxyacetophenone 0.20

TABLE 58 Dental cream against plaque (Amounts in % b.w.) IngredientsAmount Carrageenan 0.90 Glycerol 15.00 Sorbitol 70%. in water 25.00 PEG1000 3.00 Na fluoride 0.24 Tetrapotassium diphosphate 4.50 Tetrasodiumdiphosphate 1.50 Na saccarinate 0.40 Precipitated silica 20.00 Titaniumdioxide 1.00 Triclosan 0.30 Spearmint flavor (comprising 60 wt. %I-carvone and 1.00 25 wt. % I-menthol) Sodium dodecyl sulfate 1.30 Dist.water Ad 100 Benzylalcohol 0.50 Fragrance composition B 0.25

TABLE 59 Dental cream for sensitive teeth (Amounts in % b.w.)Ingredients Amount Na carboxymethylcellulose 0.70 Xanthan gum 0.50Glycerol 15.00 Sorbitol 70%. in water 12.00 Potassium nitrate 5.00Sodium monofluorophosphate 0.80 Fragrance composition B 1.00Ca-carbonate 35.00 Silicon dioxide 1.00 Sodium dodecyl sulfate (SDS)1.50 Dist. water Ad 100 PHB methyl ester and PHB propyl ester 0.20

TABLE 60 Tooth cream and mouthwash 2-in-1 product (Amounts in % b.w.)Ingredients Amount Sorbitol 40.00 Glycerol 20.00 Ethanol 5.00 Water Ad100 Na monofluorophosphate 0.75 Saccharin 0.20 Sident 9 (abrasivesilicon dioxide) 20.00 Sident 22 S (thickening silicon dioxide) 2.00Sodium carboxymethylcellulose 0.30 Sodium lauryl sulfate (SDS) 1.20Color (Suspension. 1% in water) C.I. Pigment Blue 15 0.50 Fragrancecomposition B 0.90 Solbrol M. sodium salt (methylparaben. sodium salt)0.20

TABLE 61 Ready-to-use mouthwash with fluoride (Amounts in % b.w.)Ingredients Amount Ethanol 7.00 Glycerol 12.00 Na fluoride 0.05 PluronicF-127 ® (BASF. surface-active substance) 1.40 Na phosphate buffer pH 7.01.10 Na saccharinate 0.10 Fragrance composition B 0.15 Chlorhexidinedigluconate 0.2 Dist. water to 100 Sorbic acid 0.20

TABLE 62 Sugar-free chewing-gum (Amounts in % b.w.) Ingredients AmountChewing gum base 30.00 Sorbitol. powder Ad 100 Palatinite 9.50 Xylitol2.00 Mannitol 3.00 Aspartame 0.10 Acesulfame K 0.10 Emulgum/emulsifier0.30 Sorbitol 70%. in water 14.00 Glycerol 1.00 Fragrance composition B1.50 Substance of formula (I) 0.20

TABLE 63 Bar soaps Ingredients A1 A2 A3 Sodium C12/14 Olefin Sulphonate40.0 — — Disodium Lauryl Sulphosuccinate — 40.0 — Lauryl Glucoside 15.015.0 55.0 Cetylstearyl Alcohol 12.0 12.0 12.0 Paraffin Oil (m.p. 54 to56° C.) 8.0 8.0 8.0 Maize Starch, degraded 8.0 8.0 8.0 Palmitic Acid(and) Stearic Acid 5.5 5.5 5.5 Glyceryl Stearate 2.0 2.0 2.0 CocoGlyceride 2.0 2.0 2.0 Polyquaternium-7 1.0 1.0 1.0 Perfume oil 1.0 1.01.0 Titanium dioxide 0.5 0.5 0.5 Fragrance composition B 0.05 0.05 0.05Water ad 100

TABLE 64 Syndet soaps Ingredients B1 B2 B3 Lauryl Glucoside 15.0 15.015.0 Sodium C12/14 Olefin Sulphonate 40.0 40.0 — Sodium Lauryl Sulphate— — 40.0 Paraffin Oil (m.p. 54° C.) 8.0 8.0 8.0 Tallow Fatty Alcohol 7.07.0 7.0 Maize starch 17.0 — 17.0 Dextrose — 17.0 — Coco Fatty Acids 10.010.0 10.0 Titanium dioxide 1.0 1.0 1.0 Perfume oil 1.0 1.0 1.0 Fragrancecomposition B 0.05 0.05 0.05 Water ad 100

TABLE 65 WC gel toilet blocks Ingredients C1 C2 C3 C4 C5 C6 LaurylGlucoside 5.0 1.5 1.5 1.5 5.0 1.5 Decyl Glucoside — 3.5 3.5 3.5 — 3.5Sodium Lauryl Sulphate 9.0 6.0 3.0 — 9.0 6.0 Sodium Laureth Sulphate —3.0 — — — 3.0 Cocamidopropyl Betaine — — 6.0 9.0 — — Ethanol 3.5 3.5 3.53.5 3.5 3.5 Citric Acid Mono Hydrate 3.6 3.6 3.6 3.6 3.6 3.6 SodiumHydroxide 0.5 0.5 0.5 0.5 0.5 0.5 Laurylamine + 1EO 4.5 3.0 5.0 2.5 — —Hexanediol-1,6 — 0.5 — 0.5 — Perfume oil 0.5 0.5 0.5 0.5 0.5 0.5Fragrance composition C  0.05  0.05  0.05  0.05  0.05  0.05 Water ad 100

TABLE 66 Powder detergents Ingredients E1 E2 E3 E4 E5 E6 SodiumLaureth-1 Sulphate 12.0 8.0 8.0 4.0 4.0 — Dodecylbenzene sulphonate — —4.0 8.0 4.0 8.0 Sodium Lauryl Sulphate — 4.0 — — 4.0 4.0 Coco FattyAcid, Sodium Salt 1.0 1.0 1.0 1.0 1.0 1.0 Coco Glucosides — — — 7.0 — —Laureth-5 7.0 7.0 7.0 — 7.0 7.0 Zeolite A 24.0 24.0 24.0 24.0 24.0 24.0Sodium silicate, amorphous 3.0 3.0 3.0 3.0 3.0 3.0 (modulus 1:2) Sodiumcarbonate 12.0 12.0 12.0 12.0 12.0 12.0 Polymeric polycarboxylate 5.55.5 5.5 5.5 5.5 5.5 Perborate monohydrate 16.0 16.0 16.0 16.0 16.0 16.0Tetraacetylethylenediamine 5.5 5.5 5.5 5.5 5.5 5.5Carboxymethylcellulose 0.3 0.3 0.3 0.3 0.3 0.3 Optical brightener 0.20.2 0.2 0.2 0.2 0.2 Enzyme granules (protease) 1.0 1.0 1.0 1.0 1.0 1.0Perfume oil 0.5 0.5 0.5 0.5 0.5 0.5 Fragrance composition C 0.05 0.050.05 0.05 0.05 0.05 Water ad 100

The invention claimed is:
 1. A fragrance mixture consisting of (a) atleast one compound of general formula (I)

in which R1 stands for methyl, ethyl, methoxy or ethoxy; (b) at leastone compound of general formula (II)

in which R2 stands for methyl, ethyl, methoxy or ethoxy; (c) at leastone additional fragrance, different from compounds (I) and (II) which isselected from the group consisting of melonal, triplal, ligustral,adoxal, anisaldehyde, cymal, ethylvanillin, florhydral, floralozon,helional, heliotropin, hydroxycitronellal, koavon, laurinaldehyde,canthoxal, lyral, lilial, adoxal, anisaldehyde, cumal,methyl-nonyl-acetaldehyde, citronellal, citronellyloxy-acetaldehyde,cyclamenaldehyde, bourgeonal, p-tert.-bucinal, phenylacetaldehyde,undecylenaldehyde, vanillin; 2,6,10-trimethyl-9-undecenal,3-dodecen-I-al, α-n-Amylzimtaldehyde, 4-methoxy-benz-aldehyde,benzaldehyde,3-(4-tert-butylphenyl)-propanal,2-methyl-3-(para-methoxy-phe-nylpropanal),2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal,3-phenyl-2-pro-penal,cis-/trans-3,7-dimethyl-2,6-octadien-I-al, 3,7-dimethyl-6-octen-I-al,[(3,7-dimethyl-6-octenyl)-xy]-cetaldehyde, 4-isopropylbenzyaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxyaldehyde,2-methyl-3-(isopropyl-phenyl)propanal, decyl aldehyde,2,6-dimethyl-5-heptenal; 4-(tricyclo [5.2.1.0 (2,6)]-decylidene-8)-butanal; octahydro-4,7-methano-IH-indenecarboxaldehyde;3-ethoxy-4-hydroxybenzaldehyde,para-ethyl-alpha,alpha-dimethylhydrozimtaldehyde,α-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,3,4-methylenedioxybenzaldehyde, α-n-hexyl-cinnamaldehyde,m-cymene-7-carboxaldehyde, a-methylphenylacetaldehyde,7-hydroxy-3,7-dimethyl octanal, undecenal,2,4,6-trimethyl-3-cyclohexene-I-carboxalde-hyde,4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,2,4-dimethyl-cyclohexene-3-carboxaldehyde,4-(4-hydroxy-4-methylpentyl)-3 -cylohexene-I-carboxal-dehyde,7-methoxy-3,7-dimethyloctan- 1-al, 2-methyl undecanal, 2-methyl decanal,1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal, 3-(4-ethylphenyl)-2,2-dimethylpropanal,3-(4-methoxyphenyl)-2-methylpropanal, methylno-nylacetaldehyde,2-phenylpropan- 1-al, 3-phenylprop-2-en-1-al,3-phenyl-2-pentylprop-2-en-1-al, 3-phenyl-2-hexylprop-2-en-1al,3-(4-isopropylphenyl)-2-methylpropan-1-al,3-(4-ethylphenyl)-2,2-dimethylpropan-1-al,3-(4-tert-butylphenyl)-2-methyl-propanal, 3-(3,4-Methylendioxy-phenyl)-2-methylpropan-1-al3-(4-Ethylphenyl)-2,2-dimethylpropanal,3-(3-Isopropylphenyl)-butan-1-al, 2,6-Dimethylhept-5-en-1-al,Dihydrozimtaldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5- or6-Methoxyhexahydro-4,7-methanoindan-1 or 2-carboxyaldehyde,3,7-dimethyloctan-l-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclohexene-carboxyaldehyde, 7-hydroxy-3,7-dimethyl-octanal; trans-4-decenal,2,6-nonadienal, p-tolylacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-l-yl)-2-butenal,o-methoxyzimtaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde,3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde;5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde,octanal, 2-methyl octanal,alpha-methyl-4-(I-methylethyl)benzene-acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, p-methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal,hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal,methylnonyl acetaldehyde, 1-p-menthene-q-carboxaldehyde, citral or itsmixtures, lilial citral, 1-decanal, n-undecanal, n-dodecanal,hlorhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde4-methoxybenzaldehyde, 3-methoxy-4-hydroxy-benzalde-hyde,3-ethoxy-4-hydroxybenzaldehyde, 3,4-methylendioxybenzaldehyde,3,4-dimethoxybenzaldehydebuccoxime, iso jasmone, methyl beta naphthylketone, moschus indanone, tonalid/moschus plus, α-damascone, β-damascon,δ-damascone, Iso-damascone, damascenone, damarose,methyl-dihydrojasmonate, fenchone, alphalonen, y-methylionone,fleuramone, dihydrojasmone, cis-Jasmon, iso-E-Super, methyl cedrenylketone, or methyl cedrylon, acetophenone, methyl aceto phenone,p-methoxyacetophenone, methyl-β-naphtyl ketone, benzylacetone,benzophenone, p-hydroxy phenylbutanone, celery Ketone or livescon,6-osopropyl-deca-hydro-2-naphtone, dimethyloctenone, freskomenth,4-(I-ethoxyvinyl)-3,3,5,5,-tetramethylv cyclohexanone, methylheptenone,2-(2-(4-Methyl-3-cyclohexen-1-yl) propyl)-cyclopentanone,1-(p-men-thene-6(2)-yl)-1-propanone,4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,2-Acetyl-3,3-di-methyl-norbornan,6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 4-damascol, dulcinylor cassione, gelsone, hexalone, isocyclemone E, Methylcyclocitrone,methyl lavender ketone, orivone, p-tert-butyl cyclohexanone, verdone,delphone, muscone, neobutenone, plicatone, veloutone,2,4,4,7-tetramethyl-oct-6-en-3-one, tetrameran, hedion, δ-damascone,benzylacetone, damascenone, methyl dihydrojasmonate, methyl cedrylone,hedione, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol,2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol,2-tert-Butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol,3-methyl-5-phenylpentanol, 3-phenylpropanol,4-heptenol,4-isopropylcyclohexanol, 4-tert-butycyclohexanol,6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, α-methylbenzylalcohol, α-terpineol, amylsalicylat, benzyl alcohol, benzylsalicylate, β-terpineol, butyl salicylate, citronellol, cyclohexylsalicylate, decanol, dihydromyrcenol, dimethyl benzylcarbinol, dimethylheptanol, dimethyl octanol, ethyl salicylate, ethyl vanilin, eugenol,geraniol, heptanol, hexyl salicylat, isoborneol, isoeugenol, isopulegol,menthol, myrtenol, n-hexanol, nerol, nonanol, para-menthan-7-ol,phenylethylalkohol, phenol, phenyl salicylat, tetrahydro geraniol,tetrahydro linalool, thymol, trans-2-cis-6-nonadienol,trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnamalcohol,encompass benzyl acetate, phenoxyisobutyrate,p-tert.-butylcyclohexylacetate, linalylacetate,dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate,benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate,styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramat,melusat, jasmacyclatat, benzylethyl ether, ambroxan; and, (d) at leastone solvent selected from the group consisting of ethanol, isopropylalcohol, ethylene glycol, diethylene glycol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, propylene glycol,dipropylene glycol, 1,2-butylene glycol, glycerol, diethyl phthalate,triethyl citrate, isopropyl myristate and its mixtures, wherein (i)components (a+b) and (c+d) both have an unpleasant fragrance, which isnot present when components (a+b) are added to components (c+d); and,(ii) components (a+b) are present in the mixture (a+b+c+d) in amounts offrom 0.001 to 0.1 wt. percent—calculated on the mixture.
 2. The mixtureof claim 1, consisting of as component (b) a compound of general formula(IIa)

in which R2 stands for methyl, ethyl, methoxy or ethoxy.
 3. The mixtureof claim 2 further consisting of at least one compound of formula (III)

in which R3 stands for methyl, ethyl, methoxy or ethoxy and the dottedline means a single or double bond.
 4. The mixture of claim 3 consistingof (i) about 62 to about 67% b.w. of at least one 1R,5R isomer ofcompound (I); (ii) about 14 to about 18% b.w. of at least one 1R,2R,5Risomer of compound (IIa); (iii) about 6.0 to about 7.0% b.w. of at leastone 1S,2R,5S isomer of compound (II); (iv) about 7.0 to about 9.0% b.w.of at least one 1R,5S isomer of compound (III); (v) about 4.0 to about6.0% b.w. of at least one 1R,2S,5S isomer of formula (III); and (vi)about 0.5 to about 1.0% b.w. of at least one 1R,2R,5S isomer of formula(III) on condition that the amounts add to 100% b.w.
 5. The mixture ofclaim 1, wherein said fragrance has a molecular mass of about 100 toabout 250 Dalton.
 6. The mixture of claim 1 consisting of components (a)and (b) in a ratio by weight of from about 1:99 to about 99:1.
 7. Aperfume composition comprising the fragrance mixture of claim
 1. 8. Thecomposition of claim 7, comprising about 0.001 to about 75% b.w. of thefragrance mixture.
 9. A cosmetic or household composition comprising themixture of claim
 1. 10. A method for improving the olfactory aspectsand/or for preventing unpleasant olfactory aspects of a fragrance,comprising the step of providing a fragrance in need of olfactorysupport and applying the mixture of claim 1.